KR20210104165A - Curable composition and cured object obtained by curing same - Google Patents

Abstract

(식 중, A는, CR¹⁷R¹⁸을 나타내고, B는, CR¹⁹R²⁰을 나타내고, R¹ 내지 R²⁰은 각각 독립하여, 수소, 알킬기 및 알콕시기로 이루어지는 군으로부터 선택되는 치환기를 나타내고, n은, 0 또는 1이고, 다만, n이 0일 때는 m은 1이며, n이 1일 때는 m은 0이다.)A curable composition comprising an epoxy compound represented by the following formula (1) and one selected from the group consisting of a thermal cationic polymerization initiator, an acid anhydride-based curing agent and a curing accelerator, and a photocationic polymerization initiator, and a cured product thereof This is initiated. This curable composition is useful at the point which makes it possible to produce the hardened|cured material which has high heat resistance.

(Wherein, A represents CR ¹⁷ R ¹⁸ , B represents CR ¹⁹ R ²⁰ , R ¹ to R ²⁰ each independently represent a substituent selected from the group consisting of hydrogen, an alkyl group and an alkoxy group, n is 0 or 1, provided that, when n is 0, m is 1, and when n is 1, m is 0.)

Description

A curable composition and the hardened|cured material which hardened this {CURABLE COMPOSITION AND CURED OBJECT OBTAINED BY CURING SAME}

[REFERENCE TO RELATED APPLICATIONS]

This patent application is a Japanese patent application filed earlier: Japanese Patent Application No. 2016-59069 (filed on March 23, 2016), Japanese Patent Application No. 2016-59079 (filed on: March 23, 2016), and Japanese Patent Application No. 2016-66376 (Application Date: March 29, 2016), Japanese Patent Application No. 2016-66399 (Application Date: March 29, 2016), Japanese Patent Application No. 2016-107736 (Application Date: May 30, 2016), Japanese Patent Application No. 2016-188872 (Filing Date) : September 27, 2016), Japanese Patent Application No. 2016-188873 (filed on: September 27, 2016), Japanese Special Application No. 2016-188874 (filed on: September 27, 2016), Japanese Patent Application No. 2016-188876 (filed on: 2016) September 27, 2016), Japanese Patent Application No. 2016-188879 (application date: September 27, 2016) is accompanied by a claim of priority. The entire disclosure in this patent application is incorporated herein by reference.

[Technology]

The present invention relates to a curable composition and a cured product obtained by curing the same.

As a material such as a surface protective film, an interlayer insulator, a protective insulating film for a printed orientation board, and a fiber reinforced composite material of a semiconductor element or an organic thin film element (for example, an organic electroluminescent element or an organic thin film solar cell element), an epoxy compound containing A curable composition is being used. Among these epoxy compounds, the epoxy compound which has an aromatic ring as what can obtain the hardened|cured material excellent in heat resistance etc. was used.

However, in the above applications, the compound having an aromatic ring generally has a high electron density, so the dielectric constant is high, and there is a defect in the field of electronic materials. In addition, due to problems such as coloring, the light transmittance of the resin is lowered. Therefore, in recent years, the alicyclic diamine compound which does not have an aromatic ring attracts attention. Moreover, it is calculated|required that the hardened|cured material which has high moisture resistance and heat resistance can be obtained from the curable composition used for the above uses.

Among epoxy compounds, an epoxy compound having an alicyclic skeleton is known as a cured product having excellent heat resistance and the like. For example, Patent Document 1 discloses an epoxy compound having an alicyclic skeleton having a specific structure from which a resin excellent in heat resistance or the like can be obtained.

Moreover, among these epoxy compounds, the epoxy compound which has two or more alicyclic skeletons in a molecule|numerator as what can obtain the hardened|cured material excellent in heat resistance, transparency, etc. is known. For example, Patent Document 2 discloses a curable composition containing dicyclopentadiene diepoxide or tricyclopentadiene diepoxide. Moreover, in patent document 3, the curable composition containing a diepoxy bicyclohexyl compound is disclosed. However, the epoxy compounds having an alicyclic skeleton proposed in Patent Documents 2 and 3 and the like have room for further improvement from the viewpoints of heat resistance of the cured product and weight reduction during curing.

Patent Document 1: Japanese Patent Laid-Open No. 49-126658 Patent Document 2: Japanese Patent Laid-Open No. 2004-143362 Patent Document 3: Japanese Patent Laid-Open No. 2008-31424

The present inventors, this time, one selected from the group consisting of an epoxy compound represented by the following formula (1), a thermal cationic polymerization initiator, an acid anhydride-based curing agent and a curing accelerator, and a photocationic polymerization initiator The discovery that the heat resistance of the hardened|cured material can be improved remarkably by containing it in a curable composition was acquired. The present invention is based on these findings, and an object of the present invention to be solved is to provide a curable composition from which a cured product excellent in heat resistance can be obtained.

In addition, the present inventors, by using together the epoxy compound represented by the following formula (1) and a thermal cationic polymerization initiator, can dramatically improve the heat resistance of the cured product, and also significantly reduce the weight loss during curing. found that it could be The present invention is based on these findings, and an object to be solved by the present invention is to provide a curable composition having excellent heat resistance and reduced weight loss during curing.

In addition, the present inventors have discovered that the moisture resistance and heat resistance of the cured product can be dramatically improved by using an epoxy compound represented by the following formula (1), an acid anhydride curing agent, and a curing accelerator in combination and containing it in the curable composition. got it The present invention is based on these findings, and an object to be solved by the present invention is to provide a curable composition from which a cured product excellent in moisture resistance and heat resistance can be obtained.

That is, the present invention includes the following inventions.

(1) Epoxy compound represented by the following formula (1):

(During the meal,

A represents CR ¹⁷ R ¹⁸ ,

B represents CR ¹⁹ R ²⁰ ,

R ¹ to R ²⁰ each independently represent a substituent selected from the group consisting of hydrogen, an alkyl group and an alkoxy group,

n is 0 or 1,

However, when n is 0, m is 1, and when n is 1, m is 0.)

And, a curable composition comprising one selected from the group consisting of a thermal cationic polymerization initiator, an acid anhydride-based curing agent and curing accelerator, and a photocationic polymerization initiator.

(2) Curable composition as described in (1) which further contains 1 type(s) or 2 or more types selected from the group which consists of epoxy compounds other than the epoxy compound represented by said Formula (1), an oxetane compound, and vinyl ether.

(3) the thermal cationic polymerization initiator is selected from the group consisting of an aromatic sulfonium salt-based thermal cationic polymerization initiator, an aromatic iodonium salt-based thermal cationic polymerization initiator, and an aluminum complex-based thermal cationic polymerization initiator, The curable composition according to (1) or (2).

(4) The curable composition according to (3), wherein the thermal cationic polymerization initiator is an aromatic sulfonium salt-based thermal cationic polymerization initiator.

(5) When content of the said thermal cation polymerization initiator does not contain any of an epoxy compound other than the epoxy compound represented by the said formula (1), an oxetane compound, and vinyl ether, the said curable composition said curable composition With respect to 100 parts by mass of the epoxy compound represented by the formula (1) contained in 0.1 to 15 parts by mass, the curable composition is an epoxy compound other than the epoxy compound represented by the formula (1), an oxetane compound, And when it contains 1 type or 2 or more types selected from the group which consists of vinyl ether, the epoxy compound represented by the said Formula (1), an epoxy compound other than the epoxy compound represented by the said Formula (1), an oxetane compound And the curable composition in any one of (2)-(4) which is 0.1-15 mass parts with respect to 100 mass parts of total amounts of vinyl ether.

(6) Content of the said acid anhydride type hardening|curing agent is said formula (1) contained in the said curable composition when the said curable composition does not contain epoxy compounds other than the epoxy compound represented by said Formula (1) It is 0.6-1.2 equivalent with respect to 1 equivalent of the represented epoxy compound, and when the said curable composition contains epoxy compounds other than the epoxy compound represented by the said Formula (1), the epoxy compound represented by the said Formula (1) And the curable composition as described in (2) which is 0.6-1.2 equivalent with respect to 1 equivalent of the mixture of the epoxy compound which consists of epoxy compounds other than the epoxy compound represented by the said Formula (1).

(7) the content of the curing accelerator is represented by the formula (1) contained in the curable composition when the curable composition does not contain an epoxy compound other than the epoxy compound represented by the formula (1) It is 0.1-10 mass parts with respect to 100 mass parts of epoxy compounds, When the said curable composition contains epoxy compounds other than the epoxy compound represented by the said Formula (1), the epoxy compound represented by the said Formula (1) And the curable composition as described in (2) or (6) which is 0.1-10 mass parts with respect to 100 mass parts of total amounts of epoxy compounds other than the epoxy compound represented by the said Formula (1).

(8) The curable composition according to (1), (6) or (7), wherein the curing accelerator is an imidazole-based curing accelerator.

(9) Curable composition in any one of (3)-(8) whose content of the epoxy compound represented by said Formula (1) is 10-99 mass %.

(10) The curable composition according to (1) or (2), wherein the photocationic polymerization initiator is an aromatic sulfonium salt-based photocationic polymerization initiator.

(11) When content of the said photocationic polymerization initiator does not contain any of an epoxy compound other than the epoxy compound represented by the said formula (1), an oxetane compound, and vinyl ether, the said curable composition, the said curable composition With respect to 100 parts by mass of the epoxy compound represented by the formula (1) contained in 0.1 to 20 parts by mass, the curable composition is an epoxy compound other than the epoxy compound represented by the formula (1), an oxetane compound, And when it contains 1 type or 2 or more types selected from the group which consists of vinyl ether, the epoxy compound represented by the said Formula (1), an epoxy compound other than the epoxy compound represented by the said Formula (1), an oxetane compound And the curable composition as described in (2) or (10) which is 0.1-20 mass parts with respect to 100 mass parts of total amounts of vinyl ether.

(12) Curable composition as described in (10) or (11) whose content of the epoxy compound represented by said Formula (1) is 1-50 mass %.

(13) Epoxy compounds other than the epoxy compound represented by the formula (1) are selected from the group consisting of glycidyl ether-type epoxides, glycidyl ester-type epoxides, and alicyclic epoxides, (2) The curable composition according to any one of to (12).

(14) A method for producing a cured product, comprising the step of curing the curable composition according to any one of (1) to (13).

(15) A cured product of the curable composition according to any one of (1) to (13).

ADVANTAGE OF THE INVENTION According to this invention, the curable composition which makes it possible to produce the hardened|cured material which has high heat resistance can be provided.

ADVANTAGE OF THE INVENTION According to this invention, the curable composition in which preparation of the hardened|cured material which has high heat resistance is possible can be provided. Moreover, according to the curable composition of this invention, the reduction|decrease of the weight which generate|occur|produces at the time of hardening can be suppressed very much.

ADVANTAGE OF THE INVENTION According to this invention, the curable composition which can obtain the hardened|cured material with improved heat resistance remarkably can be provided.

ADVANTAGE OF THE INVENTION According to this invention, the curable composition which makes it possible to produce the hardened|cured material which has high moisture resistance and heat resistance can be provided.

^{1 : shows the 13} C-NMR chart of the epoxy compound (A-1) manufactured in Preparation Example 1. FIG.
^{FIG. 2 : shows the 13} C-NMR chart of the epoxy compound (A-2) manufactured in Preparation Example 2. FIG.

1. Definition

In the present specification, "parts", "%", etc. indicating the blending are based on mass unless otherwise specified.

In this specification, an epoxy equivalent is defined with the mass of the epoxy compound containing 1 equivalent of an epoxy group. Here, in the case of a mixture consisting of m types of epoxy compounds (m is an integer of 2 or more), the epoxy equivalent of the mixture is,

is represented by The epoxy equivalent of an epoxy compound can be measured according to JISK7236.

2. Curable composition

The curable composition of the present invention comprises an epoxy compound represented by the following formula (1), and one selected from the group consisting of a thermal cationic polymerization initiator, an acid anhydride-based curing agent and curing accelerator, and a photocationic polymerization initiator. do it with

(During the meal,

A represents CR ¹⁵¹⁷ R ¹⁸ ,

B represents CR ¹⁹ R ²⁰ ,

R ¹ to R ²⁰ each independently represent a substituent selected from the group consisting of hydrogen, an alkyl group and an alkoxy group,

n is 0 or 1,

However, when n is 0, m is 1, and when n is 1, m is 0.)

The curable composition obtained by using dicyclopentadiene diepoxide, which is an epoxy compound having a similar alicyclic skeleton, and a thermal cationic polymerization initiator in combination has a large weight loss during curing and is difficult to handle. By using the displayed epoxy compound and a thermal cationic polymerization initiator together, the weight loss occurring at the time of curing can be greatly reduced.

Dicyclopentadiene diepoxide, which is an epoxy compound having a similar alicyclic skeleton, has low curability even when used in combination with an acid anhydride-based curing agent and a curing accelerator, making it difficult to obtain a cured product. The epoxy compound represented by the above formula (1) By using in combination with an acid anhydride curing agent and a curing accelerator, a cured product can be easily obtained, and a cured product having dramatically improved heat resistance can be obtained.

By using together the epoxy compound and a thermal cation polymerization initiator represented by the said Formula (1), the heat resistance of the hardened|cured material which hardened|cured the curable composition can be improved remarkably.

By using together the epoxy compound represented by the formula (1), an acid anhydride curing agent, and a curing accelerator, the moisture resistance and heat resistance of the cured product obtained by curing the curable composition can be dramatically improved.

The cured product obtained by curing a curable composition containing dicyclopentadiene diepoxide and a photocationic polymerization initiator, which is an epoxy compound having a similar alicyclic skeleton, has room for improvement in its heat resistance, By using an epoxy compound and a photocationic polymerization initiator together and containing it in a curable composition, the heat resistance of hardened|cured material can be improved dramatically. Moreover, transparency of hardened|cured material can be improved by using these together. Moreover, compared with the case where a thermal cationic polymerization initiator is used, since the time of hardening can be shortened remarkably, productivity can be improved.

(1) Epoxy compound

In the epoxy compound contained in the curable composition of the present invention, in the formula (1), A and B each independently ^{represent CR 15} R ¹⁶ , and R ¹ to R ¹⁶ each independently represent hydrogen, an alkyl group and an alkoxy group. A substituent selected from the group consisting of a group is represented, n is 0 or 1, and when n is 0, a crosslinked structure is not formed, but the number of carbon atoms in the alkyl group is preferably 1 to 10, and 1 to 5 more preferably. Moreover, a linear alkyl group or a branched alkyl group may be sufficient. It is preferable that it is 1-10, and, as for carbon number which this alkoxy group has, it is more preferable that it is 1-5. Particularly preferably R ¹ to R ¹⁶ are hydrogen. Moreover, the curable composition of this invention may contain the epoxy compound represented by 2 or more types of said Formula (1).

A curable composition comprising an epoxy compound represented by the formula (1) and a thermal cationic polymerization initiator, or an epoxy compound represented by the formula (1), an acid anhydride-based curing agent, and a curing accelerator. In this case, the epoxy compound represented by the formula (1) contained in the curable composition has an epoxy equivalent of preferably 85 to 600 g/eq, preferably 90 to 600 g/eq, and 85 to 300 g/eq. It is more preferable, it is more preferable that it is 90-300 g/eq, It is still more preferable that it is 90-200 g/eq. Further, other compounds described later may be included in the curable composition of the present invention, but from the viewpoint of reducing the heat resistance of the cured product and/or reduction in weight during curing, it is represented by the above formula (1) contained in the curable composition of the present invention It is preferable that content of the epoxy compound used is 10-99 mass %, It is preferable that it is 10-80 mass %, It is more preferable that it is 15-99 mass %, It is more preferable that it is 15-60 mass %.

In the case of a curable composition containing an epoxy compound represented by the formula (1) and a photocationic polymerization initiator, the epoxy compound represented by the formula (1) contained in the curable composition has an epoxy equivalent of 85 to 600 g/eq It is preferable that it is 85-300 g/eq, It is more preferable that it is 85-200 g/eq, and it is still more preferable. Although other compounds mentioned later may be contained in the curable composition of this invention, content of the epoxy compound represented by the said Formula (1) contained in the curable composition of this invention from a viewpoint of the heat resistance of hardened|cured material is 1-50 mass % It is preferable that it is, and it is more preferable that it is 5-40 mass %. In one embodiment, it is preferable that the curable composition of this invention contains epoxy compounds other than the epoxy compound represented by said Formula (1), and/or an oxetane compound further.

(2) Method for producing an epoxy compound

The epoxy compound that satisfies the formula (1) contained in the curable composition of the present invention is obtained by reacting a diolefin compound represented by the following formula (2) with a peracid such as hydrogen peroxide, peracetic acid, and perbenzoic acid. , can be synthesized.

In one embodiment, by reacting a diolefin compound represented by the following formula (3) with metachloroperbenzoic acid as a diolefin compound satisfying the formula (2), a compound satisfying the formula (1), An epoxy compound represented by the following formula (4) can be obtained. In addition, the compound of following formula (3) can be synthesize|combined by making a butadiene and dicyclopentadiene react with Diels Elder.

Further, in one embodiment, by reacting a diolefin compound represented by the following formula (5) with metachloroperbenzoic acid as a diolefin compound satisfying the formula (2), a compound satisfying the formula (1) As such, an epoxy compound represented by the following formula (6) can be obtained. In addition, the compound of following formula (5) can be synthesize|combined by making cyclopentadiene and dicyclopentadiene react with Diels Elder.

(3) Thermocationic polymerization initiator

As the cationic polymerization initiator contained in the curable composition of the present invention, a thermal cationic polymerization initiator (an initiator capable of generating cation active species by thermal energy) and a photocationic polymerization initiator (which generates cationic active species by irradiation with light or electron beams) possible initiators). By combining the epoxy compound represented by the formula (1) and the thermal cationic polymerization initiator, the heat resistance of the cured product can be further improved, and the weight loss generated during curing can be reduced. Moreover, transparency of hardened|cured material can be improved.

Examples of the thermal cationic polymerization initiator include (i) an aromatic sulfonium salt-based thermal cationic polymerization initiator, (ii) a phosphonium salt-based thermal cationic polymerization initiator, (iii) a quaternary ammonium salt-based thermal cationic polymerization initiator, (iv) ) aluminum complex-based thermal cationic polymerization initiator, (v) aromatic iodonium salt-based thermal cationic polymerization initiator, (vi) aromatic diazonium salt-based thermal cationic polymerization initiator, and (vii) pyrinidium-based thermal cationic polymerization initiator, etc. can be heard

Examples of the aromatic sulfonium salt-based thermal cationic polymerization initiator include (2-ethoxy-1-methyl-2-oxoethyl)methyl-2-naphthalenylsulfonium hexafluoroantimonate, 4-(methoxycarbonyloxy) Phenylbenzylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenyl (o -Methylbenzyl) methylsulfonium hexafluoroantimonate, 4-hydroxyphenyl (α-naphthylmethyl) methylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoro Rhoantimonate, triphenylsulfonium hexafluoroantimonate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfidebishexafluoroantimonate , hexafluoroantimonate salts such as bis[4-(diphenylsulfonio)phenyl]sulfidebishexafluoroantimonate, (2-ethoxy-1-methyl-2-oxoethyl)methyl- 2-naphthalenylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluorophosphate, 4-hydroxyphenyl (o-methylbenzyl)methylsulfonium hexafluorophosphate, 4-hydroxyphenyl ( α-naphthylmethyl) methylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, bis [4- (di (4- ( Hexafluorophosphate salts such as 2-hydroxyethoxy))phenylsulfonio)phenyl]sulfidebishexafluorophosphate and bis[4-(diphenylsulfonio)phenyl]sulfidebishexafluorophosphate , 4-hydroxyphenyl (o-methylbenzyl) methylsulfonium hexafluoroarsenate, 4-hydroxyphenylbenzylmethylsulfonium hexafluoroarsenate salts such as hexafluoroarsenate, (2- Ethoxy-1-methyl-2-oxoethyl)methyl-2-naphthalenylsulfoniumtetrafluoroborate, 4-hydroxyphenyl (o-methylbenzyl)methylsulfoniumtetrafluoroborate, 4-hydroxyphenylbenzyl Methylsulfoniumtetrafluoroborate, diphenyl-4-(phenylthio)phenylsulfoniumtetrafluoroborate, triphenylsulfoniumtetrafluoroborate, bis[4-(di(4-(2-hydroxyethoxy) ))phenylsulfonio)phenyl]sulfidebistetrafluoroborate, bis[4-(diphenylsulfonio)phene Tetrafluoroborate salts such as nyl]sulfidebistetrafluoroborate, 4-hydroxyphenyl(o-methylbenzyl)methylsulfonium trifluoromethanesulfonate, 4-hydroxyphenylbenzylmethylsulfonium trifluoro Trifluoromethanesulfonate such as methanesulfonate, trifluoromethanesulfonate such as diphenyl-4-(phenylthio)phenylsulfonium trifluoromethanesulfonate, 4-hydroxyphenyl(α-naphthylmethyl) ) bis(trifluoromethanesulfone)imide salts such as methylsulfoniumbis(trifluoromethanesulfone)imide and 4-hydroxyphenylbenzylmethylsulfoniumbis(trifluoromethanesulfone)imide, (2- Ethoxy-1-methyl-2-oxoethyl)methyl-2-naphthalenylsulfoniumtetrakis(pentafluorophenyl)borate, 4-(methoxycarbonyloxy)phenylbenzylmethylsulfoniumtetrakis(pentafluoro Phenyl) borate, 4-hydroxyphenyl (o-methylbenzyl) methylsulfonium tetrakis (pentafluorophenyl) borate, 4-hydroxyphenyl (α-naphthylmethyl) methylsulfonium tetrakis (pentafluorophenyl) ) borate, 4-hydroxyphenylbenzylmethylsulfoniumtetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfoniumtetrakis(pentafluorophenyl)borate, triphenylsulfoniumtetrakis (pentafluorophenyl) borate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfidetetrakis(pentafluorophenyl)borate, bis[4-( and tetrakis(pentafluorophenyl)borate salts such as diphenylsulfonio)phenyl]sulfidetetrakis(pentafluorophenyl)borate.

(ii) Examples of the phosphonium salt-based thermal cationic polymerization initiator include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

(iii) As a quaternary ammonium salt type thermocationic polymerization initiator, N,N-dimethyl-N-benzylanilinium hexafluoroantimonate, N,N-diethyl-N-benzylanilinium tetrafluoroborate, N ,N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzylpyridiniumtrifluoromethanesulfonic acid, N,N-dimethyl-N-(4-methoxybenzyl) ) pyridinium hexafluoroantimonate, N,N-diethyl-N-(4-methoxybenzyl)pyridinium hexafluoroantimonate, N,N-diethyl-N-(4-methoxybenzyl) ) toluidinium hexafluoroantimonate, N,N-dimethyl-N-(4-methoxybenzyl)toluidinium hexafluoroantimonate, etc. are mentioned.

(iv) Examples of the thermal cationic polymerization initiator of the aluminum complex system include aluminum carboxylate, aluminum alkoxide, aluminum chloride, aluminum (alkoxide) acetoacetic acid chelate, acetoacetonatoaluminum, and ethylacetoacetatoaluminum.

(v) As the thermocationic polymerization initiator of aromatic iodonium salt, phenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodo Niumtetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dode Sylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl- 4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methyl ethyl)phenyliodoniumtetrafluoroborate, 4-methylphenyl-4-(1-methylethyl)phenyliodoniumtetrakis(pentafluorophenyl)borate, etc. are mentioned.

(vi) As the thermal cationic polymerization initiator of aromatic diazonium salt, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate and phenyldiazonium tetrakis (pentafluorophenyl ) borate and the like.

(vii) Examples of the pyridinium-based thermal cationic polymerization initiator include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, and 1-benzyl-2 -Cyanopyridiniumtetrafluoroborate, 1-benzyl-2-cyanopyridiniumtetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridiniumhexafluorophosphate, 1 -(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridiniumtetrafluoroborate, 1-(naphthylmethyl)-2-cya Nopyridinium tetrakis (pentafluorophenyl) borate etc. are mentioned.

These thermal cation polymerization initiators may be used independently and may mix and use 2 or more types.

Among these, the thermal cationic polymerization initiator of an aromatic sulfonium salt type|system|group is more preferable, and monoaryl type thermal cationic polymerization initiators, such as 4-acetoxyphenyl dimethylsulfonium hexafluoroantimonate, are especially preferable. By combining this specific thermal cationic polymerization initiator with the epoxy compound represented by the formula (1), the heat resistance of the cured product can be further improved, and the weight loss generated during curing can be further reduced. Moreover, transparency of hardened|cured material can also be improved.

The content of the thermal cationic polymerization initiator in the curable composition of the present invention includes an epoxy compound other than the epoxy compound represented by the formula (1) described later, an oxetane compound described later, and a vinyl ether described later in the curable composition When not carrying out, it is preferable that it is 0.1-15 mass parts with respect to 100 mass parts of epoxy compounds represented by said Formula (1) contained in curable composition, and it is more preferable that it is 0.3-7 mass parts. Moreover, when curable composition contains 1 type or 2 or more types chosen from the group which consists of epoxy compounds other than the epoxy compound represented by said Formula (1), an oxetane compound, and vinyl ether, curability of this invention The content of the thermal cationic polymerization initiator in the composition is 100 parts by mass of the total amount of the epoxy compound represented by the formula (1), an epoxy compound other than the epoxy compound represented by the formula (1), an oxetane compound, and a vinyl ether , It is preferable that it is 0.1-15 mass parts, and it is more preferable that it is 0.3-7 mass parts. By making content of a thermal cation polymerization initiator into the said numerical range, the heat resistance of hardened|cured material can be improved further. Moreover, the weight loss at the time of hardening can be reduced more. Moreover, transparency of hardened|cured material can be improved more.

The cationic polymerization initiator contained in the curable composition of the present invention is selected from the group consisting of an aromatic sulfonium salt-based thermal cationic polymerization initiator, an aromatic iodonium salt-based thermal cationic polymerization initiator, and an aluminum complex-based thermal cationic polymerization initiator. more preferably. Moreover, it is more preferable that the cationic polymerization initiator contained in the curable composition of this invention is an aromatic sulfonium salt type|system|group thermal cationic polymerization initiator.

(4) acid anhydride curing agent

Examples of the acid anhydride curing agent contained in the curable composition of the present invention include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylnadic anhydride, and methyl moiety. tenyltetrahydrophthalic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, cyclohexanetricarboxylic anhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexanetetracarboxylic dianhydride, maleic anhydride, phthalic anhydride, succinic anhydride, Dodecenyl succinic anhydride, octenyl succinic anhydride, pyromellitic anhydride, trimellitic anhydride, alkylstyrene-maleic anhydride copolymer, chlorendic anhydride, polyazelaic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydro Trimellitate, glycerol trimellitate, glycerin bis(anhydrotrimellitate) monoacetate, benzophenonetetracarboxylic acid, polyadipic anhydride, polysebacic anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexa decanedioic acid) anhydride, hetic anhydride, norbornane-2,3-dicarboxylic acid anhydride, and the like.

Among these, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride are preferable from the point which can further improve the heat resistance and transparency of hardened|cured material by combining with the epoxy compound represented by the said Formula (1). The curable composition of the present invention may contain one or two or more of the above-described acid anhydride-based curing agents.

From a viewpoint of the heat resistance of hardened|cured material, content of the acid anhydride type hardening|curing agent in the curable composition of this invention is curable when curable composition does not contain epoxy compounds other than the epoxy compound represented by the said Formula (1) mentioned later. It is preferable that it is 0.5-1.5 equivalent with respect to 1 equivalent of the epoxy compound represented by the said Formula (1) contained in a composition, It is more preferable that it is 0.6-1.2 equivalent, It is still more preferable that it is 0.8-1.2 equivalent. In addition, when the curable composition contains an epoxy compound other than the epoxy compound represented by the formula (1), the content of the acid anhydride curing agent in the curable composition of the present invention is the epoxy represented by the formula (1). It is preferable that it is 0.5-1.5 equivalent with respect to 1 equivalent of the mixture of the epoxy compound which consists of an epoxy compound other than the epoxy compound represented by the said Formula (1), It is more preferable that it is 0.6-1.2 equivalent, It is more preferable that it is 0.8-1.2 It is even more preferable that it is equivalent.

(5) hardening accelerator

Examples of the curing accelerator contained in the curable composition of the present invention include triphenylphosphine, triphenylbenzylphosphonium tetraphenylborate, tetrabutylphosphonium diethylphosphorodithioate, tetraphenylphosphonium bromide, tetrabutyl Phosphonium acetate, tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, methyltri Phenylphosphonium bromide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, methyltri-n-butylphosphonium dimethyl phosphate, n-butyltriphenylphosphonium bromide, benzyltri Phosphines such as phenylphosphonium chloride and tetraphenylphosphonium tetraphenylborate and their quaternary salts, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and 1-benzyl-2-phenyl Midazole, 2-methylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2,4-diamino-6-[2- imidazoles such as methylimidazolyl-(1)]ethyl-s-triazine, 2-phenylimidazoline, and 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole; Tertiary amines such as tris(dimethylaminomethyl)phenol, benzyldimethylamine, and tetrabutylammonium bromide and their quaternary salts, 1,8-diazabicyclo(5,4,0)undecene-7,1,5- Ultra-strongly basic organic compounds such as diazabicyclo(4,3,0)nonene-5, organic carboxylate metal salts such as zinc octylate, zinc laurate, zinc stearate, and tin octylate, benzoylacetone zinc chelate, dibenzoylmethane metal-organic chelate compounds such as zinc chelate and ethyl acetoacetate zinc chelate; tetra-n-butylsulfonium-o,o-diethylphosphorodithionate; and the like.

Among these, in order that the heat resistance of hardened|cured material can be improved further by combining with the epoxy compound represented by the said Formula (1), an imidazole type hardening accelerator is especially preferable.

The curable composition of this invention may contain the above-mentioned hardening accelerator 1 type, or 2 or more types.

From the viewpoint of heat resistance of the cured product, the content of the curing accelerator in the curable composition of the present invention is determined in the curable composition when the curable composition does not contain an epoxy compound other than the epoxy compound represented by the formula (1) described later. It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of epoxy compounds represented by said Formula (1) contained, It is more preferable that it is 0.2-8 mass parts, It is still more preferable that it is 0.5-6 mass parts. In addition, when the curable composition contains an epoxy compound other than the epoxy compound represented by the formula (1), the content of the curing accelerator in the curable composition of the present invention is an epoxy compound represented by the formula (1) and It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of total amounts of epoxy compounds other than the epoxy compound represented by the said Formula (1), It is more preferable that it is 0.2-8 mass parts, It is still more preferable that it is 0.5-6 mass parts do.

(6) photocationic polymerization initiator

The photocationic polymerization initiator contained in the curable composition of the present invention generates cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet light, X-ray, and electron beam, and initiates a polymerization reaction of the cationically polymerizable compound. to do (開始) As a photocationic polymerization initiator contained in the curable composition of this invention, compounds, such as an onium salt, a metallocene complex, and an iron- allene complex, can be used, for example. As the onium salt, an aromatic sulfonium salt, an aromatic iodonium salt, an aromatic diazonium salt, an aromatic phosphonium salt, an aromatic selenium salt, etc. are used, and as these counterions, CF ₃ SO ₃ ^- , BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , and SbF ₆ ^- anions are used. Among these, in order to provide a cured product having excellent curability and good mechanical strength and adhesive strength because it has ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, an aromatic sulfonium salt-based photocationic polymerization initiator is used. more preferably. Moreover, the curable composition of this invention may contain 2 or more types of photocationic polymerization initiators.

Examples of the aromatic sulfonium salt include diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, 4,4'-bis(diphenylsulfonio)diphenylsulfidebishexafluorophosphate, 4,4'- Bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfidebishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]di Phenylsulfidebishexafluorophosphate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-toluyl)sulfony O]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4-(p-tert -Butylphenylcarbonyl)-4'-diphenylsulfonio-diphenylsulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluyl) Sulfonio-diphenylsulfidetetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, bis[ 4-(diphenylsulfonio)phenyl]sulfidebishexafluoroantimonate, (4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate, etc. are mentioned.

Examples of the aromatic iodonium salt include diphenyliodoniumtetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4-nonylphenyl) iodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium hexafluoroantimonate, bis(4-t-butylphenyl)iodonium hexafluorophosphate, etc. are mentioned.

Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium tetrafluoroborate, and 4-chlorobenzenediazonium hexafluorophosphate.

Benzyl triphenyl phosphonium hexafluoroantimonate etc. are mentioned as an aromatic phosphonium salt.

Examples of the aromatic selenium salt include triphenyl selenium hexafluorophosphate.

Examples of the iron-allene complex include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, and xylene-cyclopentadienyl iron (II) tris (tri). Fluoromethylsulfonyl)methanide and the like.

Content of the photocationic polymerization initiator in the curable composition of this invention is an epoxy compound other than the epoxy compound represented by the said Formula (1) which a curable composition is mentioned later, an oxetane compound mentioned later, and any of the vinyl ether mentioned later When not included, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of epoxy compounds represented by said Formula (1) contained in curable composition, and it is more preferable that it is 0.3-15 mass parts. Moreover, when curable composition contains 1 type or 2 or more types chosen from the group which consists of epoxy compounds other than the epoxy compound represented by said Formula (1), an oxetane compound, and vinyl ether, curability of this invention Content of the photocationic polymerization initiator in a composition is 100 mass parts of total amounts of epoxy compounds other than the epoxy compound represented by the said Formula (1), an epoxy compound represented by the said Formula (1), an oxetane compound, and vinyl ether With respect to it, it is preferable that it is 0.1-20 mass parts, and it is more preferable that it is 0.3-15 mass parts. By making content of a photocationic polymerization initiator into the said numerical range, the heat resistance of hardened|cured material can be improved further. Moreover, transparency of hardened|cured material can be improved more.

(7) Epoxy compounds other than the epoxy compound represented by the formula (1)

The curable composition of the present invention may contain an epoxy compound other than the epoxy compound represented by the above formula (1) depending on the use (in this specification, it may be called "another epoxy compound"). For example, a glycidyl ether type epoxide, a glycidyl ester type epoxide, a glycidylamine type epoxide, an alicyclic epoxide, etc., and those oligomers and a polymer are mentioned.

Examples of the glycidyl ether type epoxide include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetramethylbiphenol diglycidyl ether, hydrogenated bisphenol A diglycidyl. Glycidyl ether of dihydric phenols such as ether and brominated bisphenol A diglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris(hydroxyphenyl)methanetriglycidylether, tetrakis(hydroxyphenyl) ) Ethane tetraglycidyl ether, dinaphthyltriol triglycidyl ether, phenol novolac glycidyl ether, cresol novolac glycidyl ether, xylene skeleton containing phenol novolac glycidyl ether, dicyclopentadiene skeleton Phenol novolac glycidyl ether, biphenyl skeleton-containing phenol novolac glycidyl ether, terpene skeleton-containing phenol novolac glycidyl ether, bisphenol A novolac glycidyl ether, bisphenol F novolac glycidyl ether, bisphenol S novolac glycidyl ether, bisphenol AP novolac glycidyl ether, bisphenol C novolac glycidyl ether, bisphenol E novolac glycidyl ether, bisphenol Z novolac glycidyl ether, biphenol novolac glycidyl Diyl ether, tetramethylbisphenol A novolac glycidyl ether, dimethylbisphenol A novolac glycidyl ether, tetramethylbisphenol F novolac glycidyl ether, dimethylbisphenol F novolac glycidyl ether, tetramethylbisphenol S no Volac glycidyl ether, dimethylbisphenol S novolac glycidyl ether, tetramethyl-4,4'-biphenol novolac glycidyl ether, trishydroxyphenylmethane novolac glycidyl ether, resorcinol novolac glycidyl ether Cydyl ether, hydroquinone novolac glycidyl ether, pyrogalol novolac glycidyl ether, diisopropylidene novolac glycidyl ether, 1,1-di-4-hydroxyphenylfluorene novolac glycidyl Dil ether, phenolized polybutadiene novolac glycidyl ether, ethylphenol novolac glycidyl ether, butylphenol novolac glycidyl ether, octylphenol novolac glycidyl ether, naphthol novolac glycidyl ether, hydrogenation Glycidyl ether of polyhydric phenols such as phenol novolac glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol Glycidyl ethers of dihydric alcohols such as diglycidyl ether, cyclohexanedimethylol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, Glycidyl ether of polyhydric alcohols, such as glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, and polyglycerol polyglycidyl ether, triglycidyl isocyanurate, etc. are mentioned. have.

Examples of the glycidyl ester type epoxide include glycidyl methacrylate, phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, trimet The glycidyl ester of carboxylic acids, such as acid triglycidyl ester, and the polyepoxide of a glycidyl ester type, etc. are mentioned.

Examples of the glycidylamine epoxide include N,N-diglycidylaniline, N,N-diglycidyltoluidine, N,N,N',N'-tetraglycidyldiaminodiphenylmethane, N Glycidyl aromatic amines such as ,N,N',N'-tetraglycidyldiaminodiphenylsulfone, N,N,N',N'-tetraglycidyldiethyldiphenylmethane, bis(N,N -diglycidylaminocyclohexyl)methane (hydride of N,N,N',N'-tetraglycidyldiaminodiphenylmethane), N,N,N',N'-tetraglycidyl- 1,3-(bisaminomethyl)cyclohexane (hydride of N,N,N',N'-tetraglycidylxylylenediamine), trisglycidylmelamine, triglycidyl-p-aminophenol, N -Glycidyl heterocyclic amines, such as a glycidyl-4-glycidyloxy pyrrolidone, etc. are mentioned.

Examples of the alicyclic epoxide include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl)ether, ethylene glycol bisepoxydicyclopentyl ether, 3,4-epoxy-6-methyl Cyclohexylmethyl, 　3',4'-epoxy-6'-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclo Hexyl, 3,4-epoxy-1-methylhexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl, 3,4-epoxy-3-methylhexanecarboxylate, 3,4-epoxy-5-methyl Cyclohexylmethyl, 　3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-sulfiro-3,4-epoxy)cyclohexane- metadioxane, methylene 1,2-epoxy of bis(3,4-epoxycyclohexane), (3,3',4,4'-diepoxy)bicyclohexyl, 2,2-bis(hydroxymethyl)-1-butanol- (2-oxiranyl) cyclohexane adduct, tetrahydroindene diepoxide, etc. are mentioned. The curable composition of this invention may contain 1 or 2 or more types of epoxy compounds other than the epoxy compound represented by said Formula (1) as mentioned above.

From a viewpoint of the heat resistance of hardened|cured material, it is preferable that it is 1-90 mass % with respect to a curable composition, and, as for content of epoxy compounds other than the epoxy compound represented by said formula (1), it is more preferable that it is 5-85 mass %. do.

In one preferred embodiment, the epoxy compound other than the epoxy compound represented by the formula (1) contained in the curable composition of the present invention is a glycidyl ether epoxide, a glycidyl ester epoxide and an alicyclic It is selected from the group consisting of epoxides.

(8) reactive diluents

The curable composition of this invention may further contain the reactive diluent for viscosity-lowering. As the reactive diluent, for example, monoepoxy compound prepared by the method described in Preparation Example 4, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl ether of C12-13 mixed alcohol, 1, 2-epoxy-4-vinylcyclohexane, etc. are mentioned. The curable composition may contain the above-mentioned reactive diluent 1 type(s) or 2 or more types. The mixing ratio of the reactive diluent may be appropriately adjusted so that the curable composition containing the reactive diluent has a desired viscosity.

(9) oxetane compound

The curable composition of this invention may contain the oxetane compound. Examples of the oxetane compound include 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl) Oxetane, di[(3-ethyl-3-oxetanyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(cyclohexyloxymethyl)ox Cetane, phenol novolacoxetane, 1,3-bis[(3-ethyloxetan-3-yl)]methoxybenzene, oxetanylsilsesquioxane, oxetanylsilicate, bis[1-ethyl (3- Oxetanyl)]methylether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy ) Biphenyl, ethylene glycol (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) ) diphenoate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritoltetrakis(3-ethyl-3-oxetanylmethyl)ether, phenol novolac type oxetane, etc. can be heard The curable composition of this invention may contain the above-mentioned oxetane compound 1 type(s) or 2 or more types.

It is preferable that it is 1-90 mass %, and, as for content of the oxetane compound in the curable composition of this invention from a viewpoint of the heat resistance of hardened|cured material, it is more preferable that it is 5-85 mass %.

(10) vinyl ether compounds

The curable composition of this invention may contain the vinyl ether compound. Examples of the vinyl ether compound include monofunctional vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, Polyfunctional vinyl ethers, such as cyclohexanediol divinyl ether, trimethylol propane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, hydroxyethyl vinyl Ether, hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanediol monovinyl ether, 9-hydroxynonyl vinyl ether, propylene glycol monovinyl ether, neopentyl glycol monovinyl ether, glycerol divinyl ether, glycerol Monovinyl ether, trimethylolpropane divinyl ether, trimethylol propane monovinyl ether, pentaerythritol monovinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether Vinyl ether compounds having a hydroxyl group, such as vinyl ether, tetraethylene glycol monovinyl ether, tricyclodecanediol monovinyl ether, tricyclodecane dimethanol monovinyl ether, and 2-(2-vinyloxyethoxy)ethyl acrylate, methacryl and vinyl ethers having a heterogeneous functional group such as acid 2-(2-vinyloxyethoxy)ethyl. The curable composition of this invention may contain the above-mentioned vinyl ether compound 1 type(s) or 2 or more types.

It is preferable that it is 1-90 mass %, and, as for content of the vinyl ether compound in the curable composition of this invention from a viewpoint of the heat resistance of hardened|cured material, it is more preferable that it is 5-85 mass %.

(11) a compound having a hydroxyl group

The curable composition of this invention may contain the compound which has a hydroxyl group further. When a curable composition contains the compound which has a hydroxyl group, hardening reaction can advance slowly. As a compound which has a hydroxyl group, ethylene glycol, diethylene glycol, glycerol etc. are mentioned, for example. The curable composition of this invention may contain the compound which has an above-mentioned hydroxyl group 1 type(s) or 2 or more types.

It is preferable that it is 0.1-10 mass %, and, as for content of the compound which has a hydroxyl group in the curable composition of this invention from a viewpoint of the heat resistance of hardened|cured material, it is more preferable that it is 0.2-8 mass %.

(12) other constituents

The curable composition of this invention may contain the solvent further. As a solvent, methyl ethyl ketone, ethyl acetate, toluene, methanol, ethanol, etc. are mentioned, for example.

The curable composition of this invention is the range which does not impair the characteristic. WHEREIN: Various additives may be included. Examples of additives include fillers, silane coupling agents, mold release agents, colorants, flame retardants, antioxidants, light stabilizers and plasticizers, defoamers, light stabilizers, colorants such as pigments and dyes, plasticizers, pH adjusters, color inhibitors, gloss removers, and a deodorant, a weathering agent, an antistatic agent, a yarn friction reducing agent, a slip agent, and an ion exchange agent.

(13) Preparation of curable composition

In manufacture of the curable composition of this invention, according to the technical common knowledge widely known to a person skilled in the art, the component to further contain in a curable composition, and the preparation method of a curable composition can be selected suitably.

3. Cured material

(1) Conditions for curing

The hardened|cured material of this invention can be obtained by hardening|curing the curable composition of this invention mentioned above. Although the hardening method in particular of a curable composition is not limited, It can implement suitably by heating or light irradiation.

When curing the curable composition by heating, it is preferable to heat the curable composition in multiple stages in consideration of the reactivity height of the epoxy compound. Thereby, hardening reaction can fully advance. For example, a primary heating of 10 to 150 minutes at 100-130°C, a secondary heating of 10 to 150 minutes at 140-160°C, a third heating of 60-180 minutes at 170-200°C, 210 The curing reaction can be carried out by quaternary heating at -250°C for 10 to 150 minutes. For example, curing is performed by primary heating at 100 to 130° C. for 10 to 150 minutes, secondary heating at 140 to 200° C. for 10 to 150 minutes, and third heating at 210 to 250° C. for 10 to 150 minutes. reaction can be carried out. For example, primary heating at 80-100°C for 10-150 minutes, secondary heating at 110-120°C for 10-150 minutes, tertiary heating at 130-140°C for 60-180 minutes, 150 The curing reaction can be carried out by the fourth heating at -170°C for 10-150 minutes, the fifth heating at 180-200°C for 60-180 minutes, and the sixth heating at 210-230°C for 60-240 minutes. have. For example, primary heating at 100 to 110° C. for 10 to 150 minutes, secondary heating at 120 to 150° C. for 10 to 150 minutes, tertiary heating at 160 to 220° C. for 10 to 150 minutes, 230 The curing reaction can be carried out by quaternary heating at -250°C for 10 to 150 minutes. However, it is not limited to this, Considering characteristics, such as content of an epoxy compound and other compounds contained in a curable composition, it is preferable to change suitably and to implement.

In the case of curing the curable composition by irradiating active energy rays such as visible rays, ultraviolet rays, X rays, or electron beams, it is preferable to appropriately change the active energy ray species and conditions to be used according to the composition of the curable composition. In one embodiment, it is preferable to irradiate an ultraviolet-ray so that the accumulated light amount represented by the product of irradiation intensity and irradiation time ^{may be 10-5000 mJ/cm<2>.} By making the amount of accumulated light with respect to a curable composition into the said numerical range, the active species derived from a photocationic polymerization initiator can fully be generate|occur|produced. In addition, productivity can be improved.

(2) Use of cured product

Specific examples of the use of the curable composition and cured product of the present invention include a paint applied on a substrate such as metal, resin film, glass, paper, wood, etc., a semiconductor device or an organic thin film device (eg, an organic electroluminescent device or Surface protective film of organic thin film solar cell element), hard coat agent, coating agent such as antifouling film and antireflection film, adhesive, adhesive, lens, prism, filter, image display material, lens array, encapsulation of optical semiconductor element Various optical members such as materials, reflective mirror materials, semiconductor element encapsulants, optical waveguides, light guide plates, light diffusion plates, diffractive elements and optical adhesives, mold materials, interlayer insulators, printed orientation boards materials such as a protective insulating film for use and a fiber-reinforced composite material; and the like.

Aspect I of this invention which is one preferable embodiment of this invention includes the following invention.

(1) the following formula (1):

(During the meal,

A represents CR ¹⁷ R ¹⁸ ,

B represents CR ¹⁹ R ²⁰ ,

R ¹ to R ²⁰ each independently represent a substituent selected from the group consisting of hydrogen, an alkyl group and an alkoxy group,

n is 1,

m is 0.)

A curable composition comprising an epoxy compound represented by and a thermal cationic polymerization initiator.

(2) Curable composition as described in (1) which further contains 1 type(s) or 2 or more types selected from the group which consists of epoxy compounds other than the epoxy compound represented by said Formula (1), an oxetane compound, and vinyl ether.

(3) the cationic polymerization initiator is selected from the group consisting of an aromatic sulfonium salt-based thermal cationic polymerization initiator, an aromatic iodonium salt-based thermal cationic polymerization initiator, and an aluminum complex-based thermal cationic polymerization initiator, (1) or ( The curable composition according to 2).

(4) The curable composition according to any one of (1) to (3), wherein the cationic polymerization initiator is an aromatic sulfonium salt-based thermal cationic polymerization initiator.

(5) Curable composition in any one of (1)-(4) whose content of the epoxy compound represented by said Formula (1) is 10-99 mass %.

(6) When content of the said thermal cationic polymerization initiator does not contain any of an epoxy compound other than the epoxy compound represented by the said formula (1), an oxetane compound, and vinyl ether, the said curable composition said curable composition With respect to 100 parts by mass of the epoxy compound represented by the formula (1) contained in 0.1 to 15 parts by mass, the curable composition is an epoxy compound other than the epoxy compound represented by the formula (1), an oxetane compound, And when it contains 1 type or 2 or more types selected from the group which consists of vinyl ether, the epoxy compound represented by the said Formula (1), an epoxy compound other than the epoxy compound represented by the said Formula (1), an oxetane compound And the curable composition in any one of (1)-(5) which is 0.1-15 mass parts with respect to 100 mass parts of total amounts of vinyl ether.

(7) Epoxy compounds other than the epoxy compound represented by the formula (1) are selected from the group consisting of glycidyl ether-type epoxides, glycidyl ester-type epoxides and alicyclic epoxides, in (2) The described curable composition.

(8) A cured product of the curable composition according to any one of (1) to (7).

According to aspect I of this invention, the curable composition in which preparation of the hardened|cured material which has high heat resistance is possible can be provided. Moreover, according to the curable composition of this invention, the reduction|decrease of the weight which generate|occur|produces at the time of hardening can be suppressed very much.

According to aspect I of the present invention, the epoxy compound represented by the formula (1) contained in the curable composition of the present invention has an epoxy equivalent of preferably 90 to 600 g/eq, and more preferably 90 to 300 g/eq. It is preferable, and it is more preferable that it is 90-200 g/eq. In addition, the curable composition of the present invention may contain other compounds described later, but from the viewpoint of reducing the heat resistance of the cured product and reduction in weight during curing, the content of the epoxy compound shown above in the curable composition of the present invention is, It is preferable that it is 10-99 mass %, and it is more preferable that it is 15-99 mass %.

Aspect II of the present invention, which is one preferred embodiment of the present invention, includes the following inventions.

(1) the following formula (1):

(During the meal,

A represents CR ¹⁷ R ¹⁸ ,

B represents CR ¹⁹ R ²⁰ ,

R ¹ to R ²⁰ each independently represent a substituent selected from the group consisting of hydrogen, an alkyl group and an alkoxy group,

n is 1,

m is 0.)

A curable composition comprising an epoxy compound represented by , an acid anhydride-based curing agent, and a curing accelerator.

(2) The curable composition according to (1), further comprising an epoxy compound other than the epoxy compound represented by the formula (1).

(3) Content of the said acid anhydride type hardening|curing agent is said Formula (1) contained in the said curable composition when the said curable composition does not contain epoxy compounds other than the epoxy compound represented by said Formula (1) It is 0.6-1.2 equivalent with respect to 1 equivalent of the represented epoxy compound, and when the said curable composition contains epoxy compounds other than the epoxy compound represented by the said Formula (1), the epoxy compound represented by the said Formula (1) And the curable composition as described in (2) which is 0.6-1.2 equivalent with respect to 1 equivalent of the mixture of the epoxy compound which consists of epoxy compounds other than the epoxy compound represented by the said Formula (1).

(4) the content of the curing accelerator is represented by the formula (1) contained in the curable composition when the curable composition does not contain an epoxy compound other than the epoxy compound represented by the formula (1) It is 0.1-10 mass parts with respect to 100 mass parts of epoxy compounds, When the said curable composition contains epoxy compounds other than the epoxy compound represented by the said Formula (1), the epoxy compound represented by the said Formula (1) And the curable composition as described in (2) or (3) which is 0.1-10 mass parts with respect to 100 mass parts of mixtures of the epoxy compound which consists of epoxy compounds other than the epoxy compound represented by the said Formula (1).

(5) The curable composition according to any one of (1) to (4), wherein the curing accelerator is an imidazole-based curing accelerator.

(6) Epoxy compounds other than the epoxy compound represented by the formula (1) are selected from the group consisting of glycidyl ether epoxides, glycidyl ester epoxides and alicyclic epoxides, in (2) The described curable composition.

(7) A cured product of the curable composition according to any one of (1) to (6).

According to aspect II of this invention, the curable composition which makes it possible to produce the hardened|cured material which has high heat resistance can be provided.

According to aspect II of the present invention, the epoxy compound represented by the formula (1) contained in the curable composition of the present invention has an epoxy equivalent of preferably 90 to 600 g/eq, and more preferably 90 to 300 g/eq. It is preferable, and it is more preferable that it is 90-200 g/eq. It is preferable that it is 10-80 mass %, and, as for content of the epoxy compound represented by said Formula (1) in the curable composition of this invention, it is more preferable that it is 15-60 mass %.

Aspect III of the present invention, which is one preferred embodiment of the present invention, includes the following inventions.

(1) the following formula (1):

(During the meal,

A represents CR ¹⁷ R ¹⁸ ,

B represents CR ¹⁹ R ²⁰ ,

R ¹ to R ²⁰ each independently represent a substituent selected from the group consisting of hydrogen, an alkyl group and an alkoxy group,

n is 0,

m is 1.)

A curable composition comprising an epoxy compound represented by and a thermal cationic polymerization initiator.

(2) Curable composition as described in (1) which further contains 1 type(s) or 2 or more types selected from the group which consists of epoxy compounds other than the epoxy compound represented by said Formula (1), an oxetane compound, and vinyl ether.

(3) the cationic polymerization initiator is selected from the group consisting of an aromatic sulfonium salt-based thermal cationic polymerization initiator, an aromatic iodonium salt-based thermal cationic polymerization initiator, and an aluminum complex-based thermal cationic polymerization initiator, (1) or ( The curable composition according to 2).

(4) The curable composition according to any one of (1) to (3), wherein the cationic polymerization initiator is an aromatic sulfonium salt-based thermal cationic polymerization initiator.

(5) Curable composition in any one of (1)-(4) whose content of the epoxy compound represented by said Formula (1) is 10-99 mass %.

(6) When content of the said thermal cationic polymerization initiator does not contain any of an epoxy compound other than the epoxy compound represented by the said formula (1), an oxetane compound, and vinyl ether, the said curable composition said curable composition With respect to 100 parts by mass of the epoxy compound represented by the formula (1) contained in 0.1 to 15 parts by mass, the curable composition is an epoxy compound other than the epoxy compound represented by the formula (1), an oxetane compound, And when it contains 1 type or 2 or more types selected from the group which consists of vinyl ether, the epoxy compound represented by the said Formula (1), an epoxy compound other than the epoxy compound represented by the said Formula (1), an oxetane compound And the curable composition in any one of (2)-(5) which is 0.1-15 mass parts with respect to 100 mass parts of total amounts of vinyl ether.

(7) Epoxy compounds other than the epoxy compound represented by the formula (1) are selected from the group consisting of glycidyl ether epoxides, glycidyl ester epoxides and alicyclic epoxides, (2) to The curable composition according to any one of (7).

(8) A cured product of the curable composition according to any one of (1) to (7).

According to aspect III of the present invention, it is possible to provide a curable composition capable of obtaining a cured product having remarkably improved heat resistance.

According to aspect III of the present invention, the epoxy compound represented by the formula (1) contained in the curable composition of the present invention has an epoxy equivalent of preferably 85 to 600 g/eq, and more preferably 85 to 300 g/eq. It is preferable, and it is more preferable that it is 85-150 g/eq. In addition, although other compounds mentioned later may be contained in the curable composition of this invention, from a viewpoint of the heat resistance of hardened|cured material, content of the epoxy compound represented by the said Formula (1) contained in the curable composition of this invention is 10-99 It is preferable that it is mass %, and it is more preferable that it is 15-99 mass %.

Aspect IV of the present invention, which is one preferred embodiment of the present invention, includes the following inventions.

(1) the following formula (1):

(During the meal,

A represents CR ¹⁷ R ¹⁸ ,

B represents CR ¹⁹ R ²⁰ ,

R ¹ to R ²⁰ each independently represent a substituent selected from the group consisting of hydrogen, an alkyl group and an alkoxy group,

n is 0,

m is 1.)

A curable composition comprising an epoxy compound represented by , an acid anhydride-based curing agent, and a curing accelerator.

(2) The curable composition according to (1), further comprising an epoxy compound other than the epoxy compound represented by the formula (1).

(3) Content of the said acid anhydride type hardening|curing agent is said Formula (1) contained in the said curable composition when the said curable composition does not contain epoxy compounds other than the epoxy compound represented by said Formula (1) It is 0.6-1.2 equivalent with respect to 1 equivalent of the represented epoxy compound, and when the said curable composition contains epoxy compounds other than the epoxy compound represented by the said Formula (1), the epoxy compound represented by the said Formula (1) And the curable composition as described in (2) which is 0.6-1.2 equivalent with respect to 1 equivalent of the mixture of the epoxy compound which consists of epoxy compounds other than the epoxy compound represented by the said Formula (1).

(4) the content of the curing accelerator is represented by the formula (1) contained in the curable composition when the curable composition does not contain an epoxy compound other than the epoxy compound represented by the formula (1) It is 0.1-10 mass parts with respect to 100 mass parts of epoxy compounds, When the said curable composition contains epoxy compounds other than the epoxy compound represented by the said Formula (1), the epoxy compound represented by the said Formula (1) And the curable composition as described in (2) or (3) which is 0.1-10 mass parts with respect to 100 mass parts of mixtures of the epoxy compound which consists of epoxy compounds other than the epoxy compound represented by the said Formula (1).

(5) The curable composition according to any one of (1) to (4), wherein the curing accelerator is an imidazole-based curing accelerator.

(6) Epoxy compounds other than the epoxy compound represented by the formula (1) are selected from the group consisting of glycidyl ether epoxides, glycidyl ester epoxides and alicyclic epoxides, (2) to The curable composition according to any one of (5).

(7) A cured product of the curable composition according to any one of (1) to (6).

According to aspect IV of this invention, the curable composition which makes it possible to produce the hardened|cured material which has high moisture resistance and heat resistance can be provided.

According to aspect IV of the present invention, the epoxy compound represented by the formula (1) contained in the curable composition of the present invention has an epoxy equivalent of preferably 85 to 600 g/eq, more preferably 85 to 300 g/eq. It is preferable, and it is more preferable that it is 85-150 g/eq. It is preferable that it is 10-80 mass %, and, as for content of the epoxy compound represented by said Formula (1) in the curable composition of this invention, it is more preferable that it is 15-60 mass %.

Aspect V of the present invention, which is one preferred embodiment of the present invention, includes the following inventions.

(1) Epoxy compound represented by the following formula (1):

(During the meal,

A represents CR ¹⁷ R ¹⁸ ,

B represents CR ¹⁹ R ²⁰ ,

R ¹ to R ²⁰ each independently represent a substituent selected from the group consisting of hydrogen, an alkyl group and an alkoxy group,

n is 0 or 1,

However, when n is 0, m is 1, and when n is 1, m is 0.)

And, a curable composition comprising a photocationic polymerization initiator.

(2) Curable composition as described in (1) which further contains 1 type(s) or 2 or more types selected from the group which consists of epoxy compounds other than the epoxy compound represented by said Formula (1), an oxetane compound, and vinyl ether.

(3) The curable composition according to (1) or (2), wherein the photocationic polymerization initiator is an aromatic sulfonium salt-based photocationic polymerization initiator.

(4) Curable composition in any one of (1) (3) whose content of the epoxy compound represented by said Formula (1) is 1-50 mass %.

(5) the epoxy compound other than the epoxy compound represented by the formula (1) is selected from the group consisting of glycidyl ether-type epoxides, glycidyl ester-type epoxides, and alicyclic epoxides, (2) The curable composition according to any one of to (4).

(6) Content of the said photocationic polymerization initiator, when the said curable composition does not contain any of epoxy compounds other than the epoxy compound represented by said Formula (1), an oxetane compound, and vinyl ether, the said curable composition With respect to 100 parts by mass of the epoxy compound represented by the formula (1) contained in 0.1 to 20 parts by mass, the curable composition is an epoxy compound other than the epoxy compound represented by the formula (1), an oxetane compound, And when it contains 1 type or 2 or more types selected from the group which consists of vinyl ether, the epoxy compound represented by the said Formula (1), an epoxy compound other than the epoxy compound represented by the said Formula (1), an oxetane compound And the curable composition in any one of (2)-(5) which is 0.1-20 mass parts with respect to 100 mass parts of total amounts of vinyl ether.

(7) A cured product of the curable composition according to any one of (1) to (6).

According to the aspect V of this invention, the curable composition which can obtain the hardened|cured material which heat resistance improved dramatically can be provided.

According to aspect V of the present invention, the epoxy compound represented by the formula (1) contained in the curable composition of the present invention has an epoxy equivalent of preferably 85 to 600 g/eq, more preferably 85 to 300 g/eq. It is preferable, and it is more preferable that it is 85-200 g/eq. Although other compounds mentioned later may be contained in the curable composition of this invention, content of the epoxy compound represented by the said Formula (1) contained in the curable composition of this invention from a viewpoint of the heat resistance of hardened|cured material is 1-50 mass % It is preferable that it is, and it is more preferable that it is 5-40 mass %. In one embodiment, the curable composition of the present invention preferably further contains an epoxy compound and/or an oxetane compound other than the epoxy compound represented by the formula (1).

Example

Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not limited to these Examples.

1. Preparation Example 1: Preparation of an epoxy compound (A-1) satisfying the formula (1)

In a reaction vessel equipped with a thermometer, a stirrer, a reflux tube, and a dropping device, 23.5 kg of chloroform and 1.6 kg of a compound represented by the following formula (3) that satisfies the above formula (2) are charged, and at 0°C 4.5 kg of metachloroperbenzoic acid was dripped while stirring. It heated up to room temperature, and reacted for 12 hours.

Next, after removing metachlorobenzoic acid produced by filtration by filtration, the filtrate was washed 3 times with a 1N aqueous sodium hydroxide solution and then washed with saturated brine. After the organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, the filtrate was concentrated, and a crude product was obtained.

2 kg of toluene was added to the crude body, and it melt|dissolved at room temperature. 6 kg of heptane was dripped at this, and it crystallized. It was aged at 5°C for 1 hour. The crystallized product was collected by filtration and washed with hexane. Then, it dried under reduced pressure for 24 hours to obtain an epoxy compound (A-1) represented by the following formula (4) as a 1.4 kg white solid and satisfying the formula (1). Thus, when the epoxy equivalent of the obtained epoxy compound (A-1) was measured according to JISK7236, it was 122 g/eq. ¹³ C-NMR measurement of the structure of the obtained epoxy compound (A-1) was carried out, and it confirmed that the target epoxy compound (A-1) could be obtained. ^{A 13} C-NMR chart is shown in FIG. 1 .

2. Preparation Example 2: Synthesis of the epoxy compound (A-2) satisfying the formula (1)

In a reaction vessel equipped with a thermometer, a stirrer, a reflux tube, and a dropping device, 59.2 kg of chloroform and 4.0 kg of a compound represented by the following formula (5) that satisfies the above formula (2) were added, and stirred at -10 ° C. 10.6 kg of metachloroperbenzoic acid was dripped. It heated up to room temperature, and reacted for 12 hours.

Then, after removing metachlorobenzoic acid by-produced by filtration, the filtrate was washed with 42.0 kg of 5% sodium sulfite aqueous solution. The organic layer was further washed 4 times with 41.6 kg of 1N aqueous sodium hydroxide solution, and then washed with 48.0 kg of saturated brine. After the organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain a crude product of 5.1 kg.

3.5 kg of toluene was added to the crude body, and it melt|dissolved at room temperature. 13.7 kg of heptane was dripped at this, and it crystallized. It was aged at 5°C for 1 hour. The crystallized product was collected by filtration and washed with heptane. It dried under reduced pressure at 35 degreeC for 12 hours, and is represented by following formula (6) as 2.8 kg of white solid, and obtained the epoxy compound (A-2) which satisfy|fills said Formula (1). Thus, when the epoxy equivalent of the obtained epoxy compound (A-2) was measured according to JISK7236, it was 180 g/eq. However, the measured value (180 g/eq) of the epoxy equivalent of this epoxy compound (A-2) is the theoretical value of the epoxy equivalent of the epoxy compound (A-2) calculated from the chemical structure of the epoxy compound (A-2) ( 115 g/eq), when determining content of an acid anhydride type hardening|curing agent WHEREIN: About the epoxy compound (A-2), it was decided to use 115 g/eq which is the said theoretical value. ¹³ C-NMR measurement of the structure of the obtained epoxy compound (A-2) was carried out, and it confirmed that the target epoxy compound (A-2) could be obtained. An NMR chart is shown in FIG. 2 .

3. Preparation Example 3: Synthesis of the epoxy compound (A-3) satisfying the formula (1)

In a reaction vessel equipped with a thermometer, a stirrer, a reflux tube, and a dropping device, 59.2 kg of chloroform and 4.0 kg of a compound represented by the following formula (3), which satisfies the above formula (2), were added, and stirred at -10 ° C. 10.6 kg of metachloroperbenzoic acid was dripped. It heated up to room temperature, and reacted for 12 hours.

Then, after removing metachlorobenzoic acid by-produced by filtration, the filtrate was washed with 42.0 kg of 5% sodium sulfite aqueous solution. The organic layer was further washed 4 times with 41.6 kg of 1N aqueous sodium hydroxide solution, and then washed with 48.0 kg of saturated brine. After the organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain a crude product of 5.1 kg.

3.5 kg of toluene was added to the crude body, and it melt|dissolved at room temperature. 13.7 kg of heptane was dripped at this, and it crystallized. It was aged at 5°C for 1 hour. The crystallized product was collected by filtration and washed with heptane. It dried under reduced pressure at 35 degreeC for 12 hours, and is represented by following formula (4) as 2.8 kg of white solid, and obtained the epoxy compound (A-3) which satisfy|fills said formula (1).

4. Preparation Example 4: Preparation of reactive diluent monoepoxy compound

Preparation example of monoepoxy compound

In a reaction vessel equipped with a thermometer, a stirrer, a reflux tube, and a dropping device, 3132 g of a diolefin compound represented by the following formula (7), 3132 g of toluene, and sodium acetate are charged, and 3783 g of a 38% aqueous peracetic acid solution while stirring at -5°C was added dropwise over 5 hours. Stirring was continued at -5 degreeC as it was, and reaction was performed for 17 hours.

Next, after performing a neutralization process using 10% sodium sulfite aqueous solution, liquid separation operation was performed. Distillation was performed at a pressure of 2 hPa and a column bottom temperature of 130 to 140°C to obtain 2109 g of a colorless and transparent liquid. The obtained liquid is a monoepoxy compound for the purpose of satisfying Formula (8) in ^{that [M+H] + = 191.1439 corresponding to the theoretical structure was obtained in precise mass measurement by 13} C NMR spectrum and LC-MS. Confirmed. When the viscosity was measured using an E-type viscometer, it was 11.0 mPa·s.

I. Embodiments of aspect I of the present invention

I-1. Example I1: Preparation of curable composition containing epoxy compound (A-2) and evaluation thereof (1: Combination with other epoxy compounds and thermal cationic polymerization initiators and dicyclopentadiene diepoxide (other epoxy compounds) Comparison with (IB-1)))

(1) Example I1-1

Preparation of curable composition

As the epoxy compound (A-2), tricyclopentadiene diepoxide obtained by the method described in Preparation Example 2, other epoxy compounds (IB-2) and a thermal cationic polymerization initiator are mixed so as to have the following composition, A curable composition was obtained.

<Composition of curable composition>

75 parts by mass of epoxy compound (A-2) (tricyclopentadiene diepoxide obtained by the method described in Preparation Example 2 above)

・Other epoxy compound (IB-2) 25 parts by mass (bisphenol A liquid epoxy resin, manufactured by Shinnidetsu Chemicals, trade name YD-128)

- 2 parts by mass of thermal cationic polymerization initiator (ID-1) (aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, manufactured by Sanshin Chemical Co., Ltd., trade name: SI-150L)

<Evaluation of physical properties>

(weight reduction rate)

The curable composition obtained as mentioned above was heated at 130 degreeC for 1 hour, 150 degreeC for 1 hour, 190 degreeC for 2 hours, and 240 degreeC for 1 hour with a hot air circulation oven, and hardened|cured material was obtained. The weight loss rate was calculated as follows, and summarized in Tables I-1 and I-2.

Weight reduction rate (%) = (weight of curable composition - weight of cured product of curable composition) / weight of curable composition x 100

(Heat resistance)

The glass transition temperature of the cured product obtained as described above was measured with a differential scanning calorimeter DSC7020 manufactured by Hitachi High-Tech Sciences, heated to 30 to 300° C. at 10° C./min, and measured to determine the heat resistance of the cured product. In addition, the glass transition temperature here was measured based on "middle point glass transition temperature: T _mg " described in JIS K7121 "Method for measuring transition temperature of plastics". The measurement results are summarized in Tables I-1 and I-2.

(Comprehensive evaluation)

The comprehensive evaluation of the curable composition obtained in the said Example was evaluated according to the following evaluation criteria. The evaluation results are summarized in Tables I-1 and I-2.

(circle): It was less than 5 % of the weight loss rate, and heat resistance was 230 degreeC or more.

x: It is 5% or more of the weight loss rate and/or heat resistance less than 230 degreeC, and there existed a problem practically.

(2) Example I1-2

Except having changed the composition of the curable composition as follows, it carried out similarly to Example I1-1, and obtained the curable composition.

<Composition of curable composition>

· Epoxy compound (A-2) 60 parts by mass (tricyclopentadiene diepoxide obtained by the method described in Preparation Example 2 above)

・Other epoxy compound (IB-3) 40 parts by mass (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation, brand name: Celoxide 2021P, epoxy equivalent: 131 g/eq)

- 2 parts by mass of thermal cationic polymerization initiator (ID-1) (aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, manufactured by Sanshin Chemical Co., Ltd., trade name: SI-150L)

The curable composition obtained as mentioned above was carried out similarly to Example I1-1, and was heated, and the hardened|cured material was obtained.

The weight reduction rate and glass transition temperature of the cured product obtained as described above were measured in the same manner as in Example I1-1. The measurement results are summarized in Tables I-1 and I-2.

(3) Example I1-3

Except having changed the composition of the curable composition as shown in Tables I-1 and I-2, it carried out similarly to Example I1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was carried out similarly to Example I1-1, and was heated, and the hardened|cured material was obtained.

The weight reduction rate and glass transition temperature of the cured product obtained as described above were measured in the same manner as in Example I1-1. The measurement results are summarized in Tables I-1 and I-2.

(4) Examples I1-4 to I1-7

Except having changed the composition of the curable composition as shown in Tables I-1 and I-2, it carried out similarly to Example I1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 140 degreeC for 1 hour, 180 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot air circulation oven, and the hardened|cured material was obtained.

The weight reduction rate and glass transition temperature of the cured product obtained as described above were measured in the same manner as in Example I1-1. The measurement results are summarized in Tables I-1 and I-2.

(5) Comparative Example I1-1

Except having changed the composition of the curable composition as shown in Tables I-1 and I-2, it carried out similarly to Example I1-1, and obtained the curable composition.

The curable composition obtained as described above was heated at 140° C. for 1 hour, at 160° C. for 1 hour, at 180° C. for 1 hour, at 220° C. for 1 hour, and at 240° C. for 2 hours using a hot air circulation oven to obtain a cured product. got it

The weight reduction rate and glass transition temperature of the cured product obtained as described above were measured in the same manner as in Example I1-1. The measurement results are summarized in Tables I-1 and I-2.

(6) Comparative Examples I1-2 to I1-4

Except having changed the composition of the curable composition as shown in Tables I-1 and I-2, it carried out similarly to Example I1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 130 degreeC for 1 hour, at 150 degreeC for 1 hour, at 180 degreeC for 1 hour, and at 200 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

The weight reduction rate and glass transition temperature of the cured product obtained as described above were measured in the same manner as in Example I1-1. The measurement results are summarized in Tables I-1 and I-2.

(7) Comparative Example I1-5

Except having changed the composition of the curable composition as shown in Tables I-1 and I-2, it carried out similarly to Example I1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 110 degreeC for 1 hour, 180 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot-air circulation oven, and the hardened|cured material was obtained.

The weight reduction rate and glass transition temperature of the cured product obtained as described above were measured in the same manner as in Example I1-1. The measurement results are summarized in Tables I-1 and I-2.

(8) Comparative Example I1-6

In the curable composition, except that tricyclopentadiene diepoxide (epoxy compound (A-2)) was changed to dicyclopentadiene diepoxide (other epoxy compound (IB-1)) represented by the following formula , It carried out similarly to Example I1-1, and obtained the curable composition.

The curable composition obtained as described above was heated at 130° C. for 1 hour, at 140° C. for 1 hour, at 160° C. for 1 hour, at 190° C. for 1 hour, and at 240° C. for 2 hours in a hot air circulation oven to obtain a cured product. got it

The weight reduction rate and glass transition temperature of the cured product obtained as described above were measured in the same manner as in Example I1-1. The measurement results are summarized in Tables I-1 and I-2.

(9) Comparative Examples I1-7 to I1-10

Except having changed the composition of the curable composition as shown in Tables I-1 and I-2, it carried out similarly to Example I1-1, and obtained the curable composition.

The curable composition obtained as described above was heated at 130° C. for 1 hour, at 140° C. for 1 hour, at 160° C. for 1 hour, at 190° C. for 1 hour, and at 240° C. for 2 hours in a hot air circulation oven to obtain a cured product. got it

The weight reduction rate and glass transition temperature of the cured product obtained as described above were measured in the same manner as in Example I1-1. The measurement results are summarized in Tables I-1 and I-2.

(Comprehensive evaluation)

The comprehensive evaluation of the curable compositions obtained in Examples I1-2 to I1-7 and Comparative Examples I1-1 to I1-10 was evaluated according to the evaluation criteria described in Example I1-1. The evaluation results are summarized in Tables I-1 and I-2.

I-2. Example I2: Preparation of curable composition containing epoxy compound (A-2) and evaluation thereof (2: combination with other epoxy compounds, oxetane compounds, and thermal cationic polymerization initiators)

(1) Example I2-1

Preparation of curable composition

The tricyclopentadiene diepoxide (epoxy compound (A-2)) obtained by the said preparation example 2, an oxetane compound, and a thermal cationic polymerization initiator were mixed so that it might become the following composition, and the curable composition was obtained.

<Composition of curable composition>

- Epoxy compound (A-2) 75 parts by mass (tricyclopentadiene diepoxide obtained by the method described in Preparation Example 2 above)

・Oxetane compound (IC-1) 25 parts by mass (1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, manufactured by Toagosei Co., Ltd., brand name: Aronoxetane OXT-121)

2 parts by mass of thermal cationic polymerization initiator (ID-1) (aromatic sulfonium salt, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, manufactured by Sanshin Chemical Co., Ltd., trade name: SI-150L)

The curable composition obtained as mentioned above was heated at 100 degreeC for 1 hour, at 130 degreeC for 1 hour, at 160 degreeC for 1 hour, and at 230 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example I1-1. The measurement results are summarized in Table I-3.

(2) Examples I2-2 to I2-3

Except having changed the composition of the curable composition as shown in Table I-3, it carried out similarly to Example I2-1, and obtained the curable composition.

The curable composition obtained as mentioned above was carried out similarly to Example I2-1, and it heated and obtained the hardened|cured material.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example I2-1. The measurement results are summarized in Table I-3.

(3) Comparative Examples I2-1 to I2-3

Except having changed the composition of the curable composition as shown in Table I-3, it carried out similarly to Example I2-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 130 degreeC for 1 hour, 150 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example I2-1. The measurement results are summarized in Table I-3.

(4) Comparative Examples I2-4 and I2-5

Except having changed the composition of the curable composition as shown in Table I-3, it carried out similarly to Example I2-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 120 degreeC for 1 hour, 140 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example I1-1. The measurement results are summarized in Table I-3.

(5) Comparative Example I2-6

Except having changed the composition of the curable composition as shown in Table I-3, it carried out similarly to Example I2-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 110 degreeC for 1 hour, at 130 degreeC for 1 hour, and at 240 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

The cured product and glass transition temperature obtained as described above were measured in the same manner as in Example I1-1. The measurement results are summarized in Table I-3.

I-3. Example I3: Preparation of curable composition containing epoxy compound (A-2) and evaluation thereof (3: Combination with other epoxy compounds and thermal cationic polymerization initiators)

(1) Examples I3-1 to I3-7 and Comparative Examples I3-1 to I3-7

Except having changed the composition of the curable composition as shown in Tables I-4 and I-5 using the following components, it carried out similarly to Example I1-1, and obtained the curable composition.

(i) Epoxy compound (A-2)

Tricyclopentadiene diepoxide obtained by the method described in Preparation Example 2 was used.

(ii) other epoxy compounds (IB-1)

The dicyclopentadiene diepoxide described in Comparative Example I1-6 was used.

(iii) other epoxy compounds (IB-2)

The bisphenol A liquid epoxy resin, the Shinnidetsu Chemicals make, brand name:YD-128 was used.

(iv) other epoxy compounds (IB-3)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(v) other epoxy compounds (IB-6)

The bisphenol F-type liquid epoxy resin, the Shinnidetsu Sumi-King Chemicals make, brand name:YDF-170 was used.

(vi) other epoxy compounds (IB-8)

Triglycidyl isocyanurate, the Nissan Chemical Industry Co., Ltd. make, brand name: TEPIC-S was used.

(vii) other epoxy compounds (IB-10)

Cyclohexanedicarboxylic acid diglycidyl ester and a reagent manufactured by Tokyo Chemical Industry Co., Ltd. were used.

(viii) other epoxy compounds (IB-12)

A 1,2-epoxy-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, the Daicel company make, brand name: EHPE3150 was used.

(ix) other epoxy compounds (IB-15)

An epoxy compound prepared by the method described in Example 3 of Japanese Patent Laid-Open No. 49-126658 was used.

(x) other epoxy compounds (IB-16)

Tetrahydroindene diepoxide prepared by the method described in Japanese Patent Laid-Open No. 2012-116390 was used.

(xi) other epoxy compounds (IB-17)

1,2-epoxy-4-vinylcyclohexane, manufactured by Daicel Corporation, brand name: Celoxide 2000 was used.

(xii) thermocationic polymerization initiator (ID-1)

4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, the Sanshin Chemical Co., Ltd. make, brand name: SI-150L was used.

(2) Physical property evaluation

(Ratio of reduction in weight of the cured product of the curable composition)

The curable composition obtained as mentioned above was heated on condition of the following, and hardened|cured material was obtained.

(a) Example I3-1

The curable composition obtained as mentioned above was heated at 170 degreeC for 1 hour, at 190 degreeC for 1 hour, and at 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(b) Example I3-2

The curable composition obtained as mentioned above was heated at 110 degreeC for 1 hour, 140 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(c) Example I3-3

The curable composition obtained as mentioned above was heated at 120 degreeC for 1 hour, 180 degreeC for 1 hour, and 230 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(d) Example I3-4

The curable composition obtained as mentioned above was heated at 150 degreeC for 1 hour, 170 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(e) Example I3-5

The curable composition obtained as mentioned above was heated at 160 degreeC for 1 hour and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(f) Examples I3-6

The curable composition obtained as mentioned above was heated at 150 degreeC for 1 hour, 180 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(g) Example I3-7

The curable composition obtained as mentioned above was heated at 140 degreeC for 1 hour, 160 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(a') Comparative Example I3-1

The curable composition obtained as mentioned above was heated at 110 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(b') Comparative Example I3-2

The curable composition obtained as mentioned above was heated at 110 degreeC for 1 hour, 170 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(d') Comparative Example I3-3

The curable composition obtained as mentioned above was heated at 130 degreeC for 1 hour, 190 degreeC for 1 hour, and 230 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(c') Comparative Example I3-4

The curable composition obtained as mentioned above was heated at 120 degreeC for 1 hour, 140 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(d') Comparative Example I3-5

The curable composition obtained as mentioned above was heated at 150 degreeC for 1 hour, 170 degreeC for 1 hour, and 210 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(e') Comparative Example I3-6

The curable composition obtained as mentioned above was heated at 130 degreeC for 1 hour, 150 degreeC for 1 hour, 180 degreeC for 1 hour, and 220 degreeC for 3 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(f') Comparative Example I3-7

The curable composition obtained as mentioned above was heated at 120 degreeC for 1 hour, 130 degreeC for 1 hour, and 190 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The weight loss rate of the hardened|cured material obtained as mentioned above was carried out similarly to Example I1-1, and was computed. The measurement results are summarized in Tables I-4 and I-5.

(Heat resistance of cured product of curable composition)

The heat resistance of the cured product obtained as described above was measured in the same manner as in Example I1-1. The measurement results are summarized in Tables I-4 and I-5.

(Comprehensive evaluation)

The comprehensive evaluation of the curable composition obtained in the said Example was evaluated according to the following evaluation criteria. The evaluation results are summarized in Tables I-4 and I-5.

(circle): It was 5 % or less of weight loss rate, and it was 220 degreeC or more of heat resistance.

x: It was more than 5 % of the weight loss rate, and/or heat resistance was less than 220 degreeC, and there existed a problem practically.

I-4. Example I4: Preparation of curable composition containing epoxy compound (A-2) and its evaluation (its 4: Combination with various types of thermal cationic polymerization initiators)

(1) Examples I4-1 to I4-5 and Comparative Examples I4-1 to I4-5

Except having changed the composition of the curable composition as shown in Tables I-6 and I-7 using the following components, it carried out similarly to Example I1-1, and obtained the curable composition.

(i) Epoxy compound (A-2)

Tricyclopentadiene diepoxide obtained by the method described in Preparation Example 2 was used.

(ii) other epoxy compounds (IB-1)

The dicyclopentadiene diepoxide described in Comparative Example I1-6 was used.

(iii) other epoxy compounds (IB-2)

The bisphenol A liquid epoxy resin, the Shinnidetsu Chemicals make, brand name:YD-128 was used.

(iv) other epoxy compounds (IB-3)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(v) thermocationic polymerization initiator (ID-3)

Bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfidebishexafluoroantimonate, the ADEKA company make, Adeka Cruz SP-170 was used.

(vi) thermocationic polymerization initiator (ID-4)

Diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate, the San Apro company make, CPI-101A was used.

(vii) thermocationic polymerization initiator (ID-5)

4-methylphenyl-4-(1-methylethyl)phenyliodoniumtetrakis(pentafluorophenyl)borate, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used.

(2) Physical property evaluation

(Ratio of reduction in weight of the cured product of the curable composition)

The curable composition obtained as mentioned above was heated on condition of the following, and hardened|cured material was obtained.

(a) Example I4-1

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, 130 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(b) Example I4-2

The curable composition obtained as mentioned above was heated at 80 degreeC for 1 hour, 140 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(c) Example I4-3

The curable composition obtained as mentioned above was heated at 140 degreeC for 1 hour, 160 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(d) Example I4-4

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, 140 degreeC for 1 hour, and 200 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(e) Examples I4-5

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(a') Comparative Example I4-1

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, 130 degreeC for 1 hour, and 170 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(b') Comparative Example I4-2

The curable composition obtained as mentioned above was heated at 80 degreeC for 1 hour, 140 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(c') Comparative Example I4-3

The curable composition obtained as mentioned above was heated at 130 degreeC for 1 hour, 150 degreeC for 1 hour, and 230 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(d') Comparative Example I4-4

The curable composition obtained as mentioned above was heated at 80 degreeC for 1 hour, at 120 degreeC for 1 hour, and at 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(e') Comparative Example I4-5

The curable composition obtained as mentioned above was heated at 120 degreeC for 1 hour and 140 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The weight loss rate of the hardened|cured material obtained as mentioned above was carried out similarly to Example I1-1, and was computed. The measurement results are summarized in Tables I-6 and I-7.

(Heat resistance of cured product of curable composition)

The heat resistance of the cured product obtained as described above was measured in the same manner as in Example I1-1. The measurement results are summarized in Tables I-6 and I-7.

(Comprehensive evaluation)

The comprehensive evaluation of the curable composition obtained in the said Example was evaluated according to the following evaluation criteria. The evaluation results are summarized in Tables I-6 and I-7.

(circle): 5% or less of weight loss rate, and heat resistance was 130 degreeC or more.

x: It was more than 5 % of the weight loss rate and/or less than 130 degreeC of heat resistance, and there existed a problem practically.

I-5. Example I5: Preparation of a curable composition containing an epoxy compound (A-2) and its evaluation (its 5: Combination of various oxetane compounds and thermal cationic polymerization initiators)

(1) Examples I5-1 and I5-2 and Comparative Examples I5-1 to I5-5

Except having changed the composition of the curable composition as shown in Table I-8 using the following components, it carried out similarly to Example I1-1, and obtained the curable composition.

(i) Epoxy compound (A-2)

Tricyclopentadiene diepoxide obtained by the method described in Preparation Example 2 was used.

(ii) other epoxy compounds (IB-2)

The bisphenol A liquid epoxy resin, the Shinnidetsu Chemicals make, brand name:YD-128 was used.

(iii) other epoxy compounds (IB-3)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(iv) other epoxy compounds (IB-14)

(3,3',4,4'-diepoxy)bicyclohexyl prepared by the method described in Japanese Patent Laid-Open No. 2004-099467 was used.

(v) oxetane compound (IC-2)

3-ethyl-3-hydroxymethyloxetane, the Toagosei company make, brand name: Aronoxetane OXT-101 was used.

(vi) oxetane compound (IC-3)

Di[(3-ethyl-3-oxetanyl)methyl]ether, the Toagosei company make, brand name: Aronoxetane OXT-221 was used.

(vii) oxetane compound (IC-4)

3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, the Toagosei company make, brand name: Aronoxetane OXT-212 was used.

(viii) thermocationic polymerization initiator (ID-1)

4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, the Sanshin Chemical Co., Ltd. make, brand name: SI-150L was used.

(2) Physical property evaluation

(Ratio of reduction in weight of the cured product of the curable composition)

The curable composition obtained as mentioned above was heated on condition of the following, and hardened|cured material was obtained.

(a) Example I5-1

The curable composition obtained as described above was heated at 130° C. for 1 hour, at 140° C. for 1 hour, at 180° C. for 1 hour, at 220° C. for 1 hour, and at 240° C. for 2 hours in a hot air circulation oven to obtain a cured product. got it

(b) Example I5-2

The curable composition obtained as mentioned above was heated at 140 degreeC for 1 hour, 170 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(a') Comparative Example I5-1

The curable composition obtained as mentioned above was heated at 110 degreeC for 1 hour, 130 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(b') Comparative Example I5-2

The curable composition obtained as mentioned above was heated at 110 degreeC for 1 hour, 140 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(c') Comparative Example I5-3

The curable composition obtained as mentioned above was heated at 110 degreeC for 1 hour, at 120 degreeC for 1 hour, and at 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(d') Comparative Example I5-4

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, at 120 degreeC for 1 hour, at 150 degreeC for 1 hour, and at 230 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(e') Comparative Example I5-5

The curable composition obtained as mentioned above was heated at 130 degreeC for 1 hour, 170 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The weight loss rate of the hardened|cured material obtained as mentioned above was carried out similarly to Example I1-1, and was computed. The measurement results are summarized in Table I-8.

(Heat resistance of cured product of curable composition)

The heat resistance of the cured product obtained as described above was measured in the same manner as in Example I1-1. The measurement results are summarized in Table I-8.

(Comprehensive evaluation)

The comprehensive evaluation of the curable composition obtained in the said Example was evaluated according to the following evaluation criteria. The evaluation results are summarized in Table I-8.

(circle): 5% or less of weight loss rate, and heat resistance was 180 degreeC or more.

x: It is more than 5 % of the weight loss rate, and/or heat resistance is less than 180 degreeC, and there existed a problem practically.

II. Embodiment II of the present invention

II-1. Example II1: Preparation of a curable composition containing an epoxy compound (A-2) and its evaluation (their 1: evaluation in the case of using an acid anhydride-based curing agent)

(1) Example II1-1

Preparation of curable composition

The epoxy compound (A-2) (tricyclopentadiene diepoxide) obtained as described above, other epoxy compounds (IIB-2), an acid anhydride-based curing agent, a curing accelerator and a polymerization initiator are mixed so as to have the following composition , to obtain a curable composition.

<Composition of curable composition>

- Epoxy compound (A-2) 50 parts by mass (tricyclopentadiene diepoxide obtained by the method described in Preparation Example 2 above)

・Other epoxy compound (IIB-2) 50 parts by mass (bisphenol A liquid epoxy resin, manufactured by Shinnidetsu Chemicals, trade name: YD-128)

106 parts by mass of acid anhydride curing agent (a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, 0.9 equivalents equivalent to 1 equivalent of epoxy compound (A-2) (tricyclopentadiene diepoxide); A product made in New Japan Ika Corporation, a brand name: MH-700)

・Cure accelerator (IIC-1) 1 part by mass (2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Co., Ltd., trade name: 2E4MZ)

・Compound having a hydroxyl group 　　　5 parts by mass (ethylene glycol, manufactured by Wako Pure Chemical Industries, Ltd., reagent)

The curable composition obtained as mentioned above was heated at 120 degreeC for 2 hours, 190 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured with a differential scanning calorimeter DSC7020 manufactured by Hitachi High-Tech Sciences, heated to 30 to 300° C. at 10° C./min, and measured to determine the heat resistance of the cured product. In addition, the glass transition temperature here was measured based on "middle point glass transition temperature: T _mg " described in JIS K7121 "Method for measuring transition temperature of plastics". The measurement results are summarized in Table II-1.

(2) Comparative Example II1-1

Except having changed the composition of the curable composition as shown in Table II-1, it carried out similarly to Example II1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 100 degreeC for 2 hours and 160 degreeC for 4 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example II1-1. The measurement results are summarized in Table II-1.

(3) Comparative Example II1-2

The curing accelerator (IIC-1) in the curable composition was used as a curing accelerator (IIC-2) (tetra-n-butylsulfonium-o,o-diethylphosphorodithionate, manufactured by Nippon Chemical Industries, Ltd., trade name: Hisikorin A curable composition was obtained in the same manner as in Comparative Example II1-1 except that it was changed to PX-4 ET).

The curable composition obtained as mentioned above was heated similarly to Comparative Example II1-1, and the hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example II1-1. The measurement results are summarized in Table II-1.

(4) Comparative Example II1-3

Example II1-Example II1-, except that the acid anhydride-based curing agent in the curable composition was changed to 34 parts by mass of an amine-based curing agent (manufactured by Tokyo Chemical Industry Co., Ltd., reagent, 1,3-bisaminomethylcyclohexane) and no curing accelerator was used. It carried out similarly to 1, and obtained the curable composition.

The curable composition obtained as described above was heated at 100° C. for 1 hour, at 120° C. for 1 hour, and at 150° C. for 1 hour with a hot air circulation oven, and curing was attempted, but curing was poor due to volatilization of the curing agent during heating. , and there was a practical problem.

(5) Comparative Example II1-4

Except for changing the acid anhydride-based curing agent in the curable composition to a phenol-based curing agent (phenol novolac, manufactured by DIC, trade name: TD-2131) and changing the curing accelerator (IIC-1) to a curing accelerator (IIC-9) was carried out in the same manner as in Example II1-1 to obtain a curable composition.

The curable composition obtained as described above was heated at 100° C. for 1 hour, at 120° C. for 1 hour, and at 150° C. for 1 hour with a hot air circulation oven to attempt curing, but curing was insufficient and there was a practical problem.

II-2. Example II2: Preparation of curable composition containing epoxy compound (A-2) and evaluation thereof (2: Combination of acid anhydride-based curing agent and multiple curing accelerators)

(1) Examples II2-1 to II2-11

Preparation of curable composition

Except having changed the composition of the curable composition as shown in Tables II-2 and II-3, it carried out similarly to Example II1-1, and obtained the curable composition.

The curable composition obtained as described above was heated at 100° C. for 1 hour, at 110° C. for 1 hour, at 120° C. for 2 hours, at 190° C. for 1 hour, and at 240° C. for 2 hours using a hot air circulation oven to obtain a cured product. got it

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example II1-1. The measurement results are summarized in Tables II-2 and II-3.

(2) Examples II2 to II12

Preparation of curable composition

Except having changed the composition of the curable composition as shown in Tables II-2 and II-3, it carried out similarly to Example II1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 120 degreeC for 2 hours, 190 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example II1-1. The measurement results are summarized in Tables II-2 and II-3.

(3) Comparative Examples II2-1 to II2-2

Preparation of curable composition

Except having changed the composition of the curable composition as shown in Tables II-2 and II-3, it carried out similarly to Example II1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 100 degreeC for 2 hours and 160 degreeC for 6 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example II1-1. The measurement results are summarized in Tables II-2 and II-3.

(4) Comparative Example II2-3

In the curable composition, except for changing the epoxy compound (A-2) (tricyclopentadiene diepoxide) to the dicyclopentadiene diepoxide (other epoxy compound (IIB-1)) represented by the following formula , It carried out similarly to Example II2-1, and obtained the curable composition. In addition, the measured value (170 g/eq) of the epoxy equivalent of this epoxy compound (IIB-1) is the theoretical value of the epoxy equivalent of the epoxy compound (IIB-1) calculated from the chemical structure of the epoxy compound (IIB-1) ( 82 g/eq), when determining content of an acid anhydride type hardening|curing agent WHEREIN: About the epoxy compound (IIB-1), it was decided to use 82 g/eq which is the said theoretical value.

Although the curable composition obtained as mentioned above was heated at 100 degreeC for 2 hours and 160 degreeC for 6 hours with a hot-air circulation oven, and hardening was attempted, it was liquid and did not harden|cure.

II-3. Example II3: Preparation of a curable composition containing an epoxy compound (A-2) and its evaluation (His 3: Comparison with the case where an epoxy compound (A-2) and a compound having a hydroxyl group are not blended)

(1) Example II3-1

Except having changed the composition of the curable composition as shown in Table II-4, it carried out similarly to Example II1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 120 degreeC for 2 hours, 190 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example II1-1. The measurement results are summarized in Table II-4.

(2) Comparative Example II3-1

Except having changed the composition of the curable composition as shown in Table II-4, it carried out similarly to Example II1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 110 degreeC for 2 hours, 180 degreeC for 4 hours, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example II1-1. The measurement results are summarized in Table II-4.

Each component used in Tables II-2 to II-4 for preparation of each curable composition is as follows.

Other epoxy compounds (IIB-3): 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation, brand name: Celoxide 2021P

Other epoxy compounds (IIB-4): Cresol novolac type epoxy resin, manufactured by DIC Corporation, brand name: EPICLON N-660

Curing accelerator (IIC-3): 1,2-dimethylimidazole, manufactured by Shikoku Chemical Co., Ltd., brand name: 1.2DMZ

Curing accelerator (IIC-4): 1-benzyl-2-phenylimidazole, manufactured by Shikoku Chemical Co., Ltd., brand name: 1B2PZ

Curing accelerator (IIC-5): 1-cyanoethyl-2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Co., Ltd., brand name: 2E4MZ-CN

Curing accelerator (IIC-6): 1,8-diazabicyclo (5,4,0) undecene-7, manufactured by Tokyo Chemical Industry Co., Ltd., reagent

Curing accelerator (IIC-7): tetrabutylammonium bromide, manufactured by Tokyo Kasei Kogyo Co., Ltd., reagent

Curing accelerator (IIC-8): methyl tri-n-butylphosphonium dimethyl phosphate, manufactured by Nippon Chemical Co., Ltd., brand name: Hisikorin PX-4MP

Curing accelerator (IIC-9): triphenylphosphine, manufactured by Tokyo Kasei Kogyo Co., Ltd., reagent

Curing accelerator (IIC-10): 2-methylimidazole, manufactured by Shikoku Chemical Co., Ltd., brand name: 2MI

II-4. Example II4: Preparation of curable composition containing epoxy compound (A-2) and evaluation thereof (4: Combination of various other epoxy compounds and acid anhydride-based curing agents)

(1) Examples II4-1 to II4-13 and Comparative Examples II4-1 to II4-14

Except having changed the composition of the curable composition as shown in Tables II-5 to II-7 using the following components, it carried out similarly to Example II1-1, and obtained the curable composition.

(i) Epoxy compound (A-2)

Tricyclopentadiene diepoxide obtained by the method described in Preparation Example 2 was used.

(ii) other epoxy compounds (IIB-2)

The bisphenol A liquid epoxy resin, the Shinnidetsu Chemicals make, brand name:YD-128 was used.

(iii) other epoxy compounds (IIB-3)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(iv) other epoxy compounds (IIB-5)

A phenol novolak-type epoxy resin, the Shinnidetsu Chemicals make, brand name:YDPN-638 was used.

(v) other epoxy compounds (IIB-6)

The bisphenol F-type liquid epoxy resin, the Shinnidetsu Sumi-King Chemicals make, brand name:YDF-170 was used.

(vi) other epoxy compounds (IIB-7)

Hydrogenated bisphenol A liquid epoxy resin, the Mitsubishi Chemical Corporation make, brand name:YX8000 was used.

(vii) other epoxy compounds (IIB-8)

Triglycidyl isocyanurate, the Nissan Chemical Industry Co., Ltd. make, brand name: TEPIC-S was used.

(viii) other epoxy compounds (IIB-9)

Tetramethylene glycol diglycidyl ether and a reagent manufactured by Tokyo Chemical Industry Co., Ltd. were used.

(ix) other epoxy compounds (IIB-10)

Cyclohexanedicarboxylic acid diglycidyl ester and a reagent manufactured by Tokyo Chemical Industry Co., Ltd. were used.

(x) other epoxy compounds (IIB-11)

Vinyl cyclohexene dioxide and a reagent manufactured by Sigma Aldorich were used.

(xi) other epoxy compounds (IIB-12)

A 1,2-epoxy-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, the Daicel company make, brand name: EHPE3150 was used.

(xii) other epoxy compounds (IIB-13)

Limonene dioxide and a reagent manufactured by Sigma Aldorich were used.

(xiii) other epoxy compounds (IIB-14)

(3,3',4,4'-diepoxy)bicyclohexyl, the Daicel company make, brand name: Celoxide 8000 was used.

(xiv) other epoxy compounds (IIB-15)

An epoxy compound prepared by the method described in Example 3 of Japanese Patent Laid-Open No. 49-126658 was used.

(xv) other epoxy compounds (IIB-16)

Tetrahydroindene diepoxide prepared by the method described in Japanese Patent Laid-Open No. 2012-116390 was used.

(xvi) other epoxy compounds (IIB-18)

A monoepoxy compound prepared by the method described in Preparation Example 4 was used.

(xvii) acid anhydride curing agent

The mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, the Shin-Nippon Ikas company make, brand name:MH-700 was used.

(xviii) curing accelerator (IIC-1)

2-ethyl-4-methylimidazole, the Shikoku Chemical Co., Ltd. make, brand name:2E4MZ was used.

(xix) hardening accelerator (IIC-6)

1,8-diazabicyclo(5,4,0)undecene-7, manufactured by Tokyo Chemical Industry Co., Ltd. and reagent was used.

(xx) a compound having a hydroxyl group

Ethylene glycol, the Wako Pure Chemical Industries, Ltd. product, and reagent were used.

(2) Physical property evaluation

(Heat resistance of cured product of curable composition)

The curable composition obtained as mentioned above was heated on condition of the following, and hardened|cured material was obtained.

(a) Example II4-1

The curable composition obtained as mentioned above was heated at 120 degreeC for 1 hour, 150 degreeC for 1 hour, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(b) Example II4-2

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(c) Example II4-3

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 130 degreeC for 1 hour, and 160 degreeC for 2 hours with a hot-air circulation oven, and the hardened|cured material was obtained.

(d) Example II4-4

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 130 degreeC for 1 hour, and 170 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(e) Examples II4-5

The curable composition obtained as mentioned above was heated at 100 degreeC for 1 hour, 140 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(f) Examples II4-6

The curable composition obtained as mentioned above was heated at 60 degreeC for 1 hour, at 110 degreeC for 1 hour, at 160 degreeC for 1 hour, and at 240 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(g) Example II4-7

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 130 degreeC for 1 hour, and 160 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(h) Examples II4-8

The curable composition obtained as mentioned above was heated at 60 degreeC for 1 hour, at 120 degreeC for 1 hour, at 160 degreeC for 1 hour, and at 210 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(i) Examples II4-9

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, 130 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(j) Examples II4-10

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, 180 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(k) Examples II4-11

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(l) Examples II4-12

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(m) Examples II4-13

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour and 180 degreeC with a hot-air circulation oven for 2 hours, and the hardened|cured material was obtained.

(a') Comparative Example II4-1

The curable composition obtained as mentioned above was heated at 120 degreeC for 1 hour, 150 degreeC for 1 hour, and 170 degreeC for 2 hours with a hot-air circulation oven, and the hardened|cured material was obtained.

(b') Comparative Example II4-2

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(c') Comparative Example II4-3

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 130 degreeC for 1 hour, and 160 degreeC for 2 hours with a hot-air circulation oven, and the hardened|cured material was obtained.

(d') Comparative Example II4-4

The curable composition obtained as mentioned above was heated at 80 degreeC for 1 hour, 130 degreeC for 1 hour, and 170 degreeC for 2 hours with a hot air circulation oven, and the hardened|cured material was obtained.

(e') Comparative Example II4-5

The curable composition obtained as mentioned above was heated at 100 degreeC for 1 hour, 140 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(f') Comparative Example II4-6

The curable composition obtained as mentioned above was heated at 60 degreeC for 1 hour, at 110 degreeC for 1 hour, at 160 degreeC for 1 hour, and at 240 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(g') Comparative Example II4-7

The curable composition obtained as mentioned above was heated at 80 degreeC for 1 hour, 120 degreeC for 1 hour, and 150 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(h') Comparative Example II4-8

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, at 100 degreeC for 1 hour, at 190 degreeC for 1 hour, and at 240 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(i') Comparative Example II4-9

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, 130 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(j') Comparative Example II4-10

The curable composition obtained as described above was heated at 110° C. for 1 hour, at 120° C. for 1 hour, at 130° C. for 1 hour, at 150° C. for 1 hour, and at 240° C. for 1 hour using a hot air circulation oven to obtain a cured product. got it

(k') Comparative Example II4-11

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(l') Comparative Example II4-12

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(m') Comparative Example II4-13

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(n') Comparative Example II4-14

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour and 180 degreeC with a hot-air circulation oven for 2 hours, and the hardened|cured material was obtained.

The heat resistance of the cured product obtained as described above was measured in the same manner as in Example II1-1. The measurement results are put together in Tables II-5 to II-7.

III. Embodiment III of the present invention

III-1. Example III1: Preparation of curable composition containing epoxy compound (A-1) and evaluation thereof (1: Combination of other epoxy compounds and thermal cationic polymerization initiators)

(1) Example III1-1

Preparation of curable composition

The epoxy compound (A-1) obtained as mentioned above and a thermal cation polymerization initiator were mixed so that it might become the following composition, and the curable composition was obtained.

<Composition of curable composition>

- 100 parts by mass of epoxy compound (A-1) (obtained by the method described in Preparation Example 1)

- Thermal cationic polymerization initiator (IIID-1) 2 parts by mass (aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, manufactured by Sanshin Chemical Co., Ltd., trade name: SI-150L)

The curable composition obtained as described above is poured into a mold of 3 mm × 30 mm × 130 mm, and is heated by a hot air circulation oven at 100° C. for 1 hour, at 110° C. for 1 hour, at 130° C. for 1 hour, at 150° C. for 1 hour, It heated at 180 degreeC for 2 hours and 220 degreeC for 3 hours, and obtained the hardened|cured material.

The glass transition temperature of the cured product obtained as described above was measured with a thermomechanical analyzer (Hitachi Hi-Tech Science, trade name: TMA7100) at a temperature of 30 to 300° C. at 10° C./min, and the temperature of the cured product was determined. In addition, the glass transition temperature here was made into the intersection of the tangent of the straight line on the low temperature side and the tangent of the straight line on the high temperature side. The measurement results are summarized in Table III-1.

(2) Example III1-2

Except having changed the composition of the curable composition as follows, it carried out similarly to Example III1-1, and obtained the curable composition.

<Composition of curable composition>

- Epoxy compound (A-1) 75 parts by mass (obtained by the method described in Preparation Example 1)

・Other epoxy compound (IIIB-1) 25 parts by mass (bisphenol A liquid epoxy resin, manufactured by Shinnidetsu Chemicals, trade name: YD-128)

- Thermal cationic polymerization initiator (IIID-1) 2 parts by mass (aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, manufactured by Sanshin Chemical Co., Ltd., trade name: SI-150L)

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and was heated at 100°C for 1 hour, at 110°C for 1 hour, at 130°C for 1 hour, and at 150°C by a hot air circulation oven. It heated at 180 degreeC for 1 hour, and 220 degreeC for 5 hours, and obtained hardened|cured material.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III1-1. The measurement results are summarized in Table III-1.

(3) Examples III1-3 and III1-4

Except having changed the composition of the curable composition as shown in Table III-1, it carried out similarly to Example III1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was carried out similarly to Example III1-2, and it heated, and obtained the hardened|cured material.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III1-1. The measurement results are summarized in Table III-1.

(4) Example III1-5

Except having changed the composition of the curable composition as follows, it carried out similarly to Example III1-1, and obtained the curable composition.

<Composition of curable composition>

- Epoxy compound (A-1) 75 parts by mass (obtained by the method described in Preparation Example 1)

・Other epoxy compound (IIIB-2) 25 parts by mass (3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, manufactured by Daicel, trade name: Celoxide 2021P)

・Thermal cationic polymerization initiator (IIID-1) 1 part by mass (aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, manufactured by Sanshin Chemical Co., Ltd., trade name: SI-150L)

The curable composition obtained as mentioned above was carried out similarly to Example III1-1, and was heated, and the hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III1-1. The measurement results are summarized in Table III-1.

(5) Examples III1-6 and III1-7

Except having changed the composition of the curable composition as shown in Table III-1, it carried out similarly to Example III1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was carried out similarly to Example III1-1, and was heated, and the hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III1-1. The measurement results are summarized in Table III-1.

(6) Comparative Examples III1-1 to III1-3

Except having changed the composition of the curable composition as shown in Table III-1, it carried out similarly to Example III1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was carried out similarly to Example III1-2, and it heated, and obtained the hardened|cured material.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III1-1. The measurement results are summarized in Table III-1.

(7) Comparative Examples III1-4 and III1-5

Except having changed the composition of the curable composition as shown in Table III-1, it carried out similarly to Example III1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was carried out similarly to Example III1-1, and was heated, and the hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III1-1. The measurement results are summarized in Table III-1.

III-2. Example III2: Preparation of curable composition containing epoxy compound (A-1) and its evaluation (2: Combination with other various epoxy compounds and thermal cationic polymerization initiators)

(1) Example III2-1

Except having changed the composition of the curable composition as follows, it carried out similarly to Example III1-1, and obtained the curable composition.

<Composition of curable composition>

- 50 parts by mass of epoxy compound (A-1) (obtained by the method described in Preparation Example 1)

・Other epoxy compounds (IIIB-3) 50 parts by mass (cresol novolak type epoxy resin, manufactured by DIC, trade name: N-660)

- Thermal cationic polymerization initiator (IIID-1) 2 parts by mass (aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, manufactured by Sanshin Chemical Co., Ltd., trade name: SI-150L)

The curable composition obtained as described above was heated at 110° C. for 1 hour, at 130° C. for 1 hour, at 150° C. for 1 hour, at 180° C. for 2 hours, and at 220° C. for 3 hours in a hot air circulation oven to obtain a cured product. got it

The glass transition temperature of the cured product obtained as described above was measured with a differential scanning calorimeter DSC7000X manufactured by Hitachi High-Tech Sciences Co., Ltd., heated to 30 to 300°C at 10°C/min, and measured to obtain the heat resistance of the cured product. In addition, the glass transition temperature here was measured based on "middle point glass transition temperature: T _mg " described in JIS K7121 "Method for measuring transition temperature of plastics". The measurement results are summarized in Table III-2.

(2) Example III2-2

Except having changed the composition of the curable composition as follows, it carried out similarly to Example III1-1, and obtained the curable composition.

<Composition of curable composition>

- 50 parts by mass of epoxy compound (A-1) (obtained by the method described in Preparation Example 1)

・Other epoxy compounds (IIIB-4) 50 parts by mass (phenol novolak type epoxy resin, manufactured by Shinnidetsu Chemicals Co., Ltd., trade name: YDPN-638)

- Thermal cationic polymerization initiator (IIID-1) 2 parts by mass (aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, manufactured by Sanshin Chemical Co., Ltd., trade name: SI-150L)

The curable composition obtained as mentioned above was carried out similarly to Example III2-1, and was heated, and the hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III2-1. The measurement results are summarized in Table III-2.

(3) Comparative Examples III2-1 to III2-4

Except having changed the composition of the curable composition as shown in Table III-2, it carried out similarly to Example III1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was carried out similarly to Example III2-1, and was heated, and the hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III2-1. The measurement results are summarized in Table III-2.

III-3. Example III3: Preparation of curable composition containing epoxy compound (A-1) and evaluation thereof (3: Combination of oxetane compound and thermal cationic polymerization initiator thereof)

(1) Example III3-1

Except having changed the composition of the curable composition as follows, it carried out similarly to Example III1-1, and obtained the curable composition.

<Composition of curable composition>

- 50 parts by mass of epoxy compound (A-1) (obtained by the method described in Preparation Example 1)

50 parts by mass of oxetane compound (IIIC-1) (1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, manufactured by Toagosei Corporation, trade name: Aronoxetane OXT-121)

・Thermal cationic polymerization initiator (IIID-1) 1 part by mass (aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, manufactured by Sanshin Chemical Co., Ltd., trade name: SI-150L)

The curable composition obtained as described above is poured into a mold of 3 mm × 30 mm × 130 mm, and is heated by a hot air circulation oven at 110° C. for 1 hour, at 130° C. for 1 hour, at 150° C. for 1 hour, at 180° C. for 2 hours, It heated at 220 degreeC for 3 hours, and obtained hardened|cured material.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III1-1. The measurement results are summarized in Table III-3.

(2) Comparative Examples III3-1 and III3-2

Except having changed the composition of the curable composition as shown in Table III-3, it carried out similarly to Example III1-1, and obtained the curable composition.

The curable composition obtained as mentioned above was carried out similarly to Example III3-1, and was heated, and the hardened|cured material was obtained.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III1-1. The measurement results are summarized in Table III-3.

III-4. Example III4: Preparation of a curable composition containing an epoxy compound (A-1) and its evaluation (its 4: Combination with other various epoxy compounds and thermal cationic polymerization initiators)

(1) Examples III4-1 to III4-5 and Comparative Examples III4-1 to 4 III-5

Except having changed the composition of the curable composition as shown in Table III-4 using the following components, it carried out similarly to Example III1-1, and obtained the curable composition.

(i) Epoxy compound (A-1)

The epoxy compound (A-1) obtained by the method described in Preparation Example 1 was used.

(ii) other epoxy compounds (IIIB-2)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(iii) other epoxy compounds (IIIB-5)

The bisphenol F-type liquid epoxy resin, the Shinnidetsu Sumi-King Chemicals make, brand name:YDF-170 was used.

(iv) other epoxy compounds (IIIB-6)

Hydrogenated bisphenol A liquid epoxy resin, the Mitsubishi Chemical Corporation make, brand name:YX8000 was used.

(v) other epoxy compounds (IIIB-7)

Triglycidyl isocyanurate, the Nissan Chemical Industry Co., Ltd. make, brand name: TEPIC-S was used.

(vi) other epoxy compounds (IIIB-11)

A 1,2-epoxy-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, the Daicel company make, brand name: EHPE3150 was used.

(vii) other epoxy compounds (IIIB-15)

1,2-epoxy-4-vinylcyclohexane, manufactured by Daicel Corporation, brand name: Celoxide 2000 was used.

(viii) thermocationic polymerization initiator (IIID-1)

Aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, the Sanshin Chemical Co., Ltd. make, brand name:SI-150L was used.

(2) Physical property evaluation

The curable composition obtained as mentioned above was heated on condition of the following, and hardened|cured material was obtained.

(a) Example III4-1

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 170° C. for 1 hour, and at 220° C. for 2 hours with a hot air circulation oven. got the cargo.

(b) Example III4-2

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 160°C for 1 hour, at 180°C for 1 hour, and at 220°C for 2 hours using a hot air circulation oven, got the cargo.

(c) Example III4-3

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 140° C. for 1 hour, and at 220° C. for 2 hours using a hot air circulation oven. got the cargo.

(d) Example III4-4

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 170° C. for 1 hour, and at 230° C. for 2 hours with a hot air circulation oven. got the cargo.

(e) Example III4-5

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 140° C. for 1 hour, and at 220° C. for 2 hours using a hot air circulation oven. got the cargo.

(a') Comparative Example III4-1

The curable composition obtained as mentioned above was poured into a mold similarly to Example III1-1, and it heated at 120 degreeC for 1 hour and 220 degreeC with a hot-air circulation oven for 2 hours, and obtained hardened|cured material.

(b') Comparative Example III4-2

The curable composition obtained as mentioned above was poured into a metal mold|die similarly to Example III1-1, and it heated at 110 degreeC for 1 hour and 240 degreeC with a hot air circulation oven for 2 hours, and obtained hardened|cured material.

(c') Comparative Example III4-3

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 110° C. for 1 hour, at 170° C. for 1 hour, and at 220° C. for 2 hours with a hot air circulation oven, got the cargo.

(d') Comparative Example III4-4

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 130° C. for 1 hour, at 190° C. for 1 hour, and at 230° C. for 2 hours with a hot air circulation oven. got the cargo.

(e') Comparative Example III4-5

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 140° C. for 1 hour, and at 220° C. for 2 hours using a hot air circulation oven. got the cargo.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III2-1. The measurement results are summarized in Table III-4.

III-5. Example III5: Preparation of curable composition containing epoxy compound (A-1) and evaluation thereof (5: combination with other various epoxy compounds, various oxetane compounds, and thermal cationic polymerization initiators)

(1) Examples III5-1 to III5-4 and Comparative Examples III5-1 to III5-10

Except having changed the composition of the curable composition as shown in Tables III-5 and III-6 using the following components, it carried out similarly to Example III1-1, and obtained the curable composition.

(i) Epoxy compound (A-1)

The epoxy compound (A-1) obtained by the method described in Preparation Example 1 was used.

(ii) other epoxy compounds (IIIB-1)

The bisphenol A liquid epoxy resin, the Shinnidetsu Chemicals make, brand name:YD-128 was used.

(iii) other epoxy compounds (IIIB-2)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(iv) other epoxy compounds (IIIB-13)

(3,3',4,4'-diepoxy)bicyclohexyl, the Daicel company make, brand name: Celoxide 8000 was used.

(v) oxetane compound (IIIC-1)

1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, the Toagosei company make, brand name: Aronoxetane OXT-121 was used.

(vi) oxetane compound (IIIC-2)

3-ethyl-3-hydroxymethyloxetane, the Toagosei company make, brand name: Aronoxetane OXT-101 was used.

(vii) oxetane compound (IIIC-3)

Di[(3-ethyl-3-oxetanyl)methyl]ether, the Toagosei company make, brand name: Aronoxetane OXT-221 was used.

(viii) oxetane compound (IIIC-4)

3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, the Toagosei company make, brand name: Aronoxetane OXT-212 was used.

(ix) thermocationic polymerization initiator (IIID-1)

Aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, the Sanshin Chemical Co., Ltd. make, brand name:SI-150L was used.

(2) Physical property evaluation

The curable composition obtained as mentioned above was heated on condition of the following, and hardened|cured material was obtained.

(a) Example III5-1

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and was heated at 70°C for 1 hour, at 120°C for 1 hour, at 150°C for 1 hour, and at 230°C by a hot air circulation oven. It heated for 2 hours and obtained hardened|cured material.

(b) Example III5-2

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and was heated at 70°C for 1 hour, at 120°C for 1 hour, at 150°C for 1 hour, and at 230°C by a hot air circulation oven. It heated for 2 hours and obtained hardened|cured material.

(c) Example III5-3

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and was heated at 70°C for 1 hour, at 120°C for 1 hour, at 150°C for 1 hour, and at 230°C by a hot air circulation oven. It heated for 2 hours and obtained hardened|cured material.

(d) Example III5-4

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 140° C. for 1 hour, and at 220° C. for 2 hours using a hot air circulation oven. got the cargo.

(a') Comparative Example III5-1

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 140° C. for 1 hour, and at 220° C. for 2 hours with a hot air circulation oven. got the cargo.

(b') Comparative Example III5-2

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 140° C. for 1 hour, and at 220° C. for 2 hours using a hot air circulation oven. got the cargo.

(c') Comparative Example III5-3

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 110° C. for 1 hour, at 130° C. for 1 hour, and at 240° C. for 2 hours with a hot air circulation oven, got the cargo.

(d') Comparative Example III5-4

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 110° C. for 1 hour, at 130° C. for 1 hour, and at 220° C. for 2 hours with a hot air circulation oven, got the cargo.

(e') Comparative Example III5-5

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 110° C. for 1 hour, at 140° C. for 1 hour, and at 240° C. for 2 hours with a hot air circulation oven, got the cargo.

(f') Comparative Example III5-6

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 110° C. for 1 hour, at 120° C. for 1 hour, and at 220° C. for 2 hours using a hot air circulation oven, got the cargo.

(g') Comparative Example III5-7

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and was heated at 70°C for 1 hour, at 120°C for 1 hour, at 150°C for 1 hour, and at 230°C by a hot air circulation oven. It heated for 2 hours and obtained hardened|cured material.

(h') Comparative Example III5-8

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and was heated at 70°C for 1 hour, at 120°C for 1 hour, at 150°C for 1 hour, and at 230°C by a hot air circulation oven. It heated for 2 hours and obtained hardened|cured material.

(I') Comparative Example III5-9

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 130° C. for 1 hour, at 170° C. for 1 hour, and at 220° C. for 2 hours with a hot air circulation oven. got the cargo.

(j') Comparative Example III5-10

The curable composition obtained as mentioned above was poured into a mold similarly to Example III1-1, and it heated at 125 degreeC for 1 hour and 220 degreeC with a hot air circulation oven for 2 hours, and obtained hardened|cured material.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III2-1. The measurement results are summarized in Tables III-5 and III-6.

III-6. Example III6: Preparation of curable composition containing epoxy compound (A-1) and its evaluation (its 6: Combination with various thermal cationic polymerization initiators)

(1) Examples III6-1 to III6-4 and Comparative Examples III6-1 to III6-4

Except having changed the composition of the curable composition as shown in Table III-7 using the following components, it carried out similarly to Example III1-1, and obtained the curable composition.

(i) Epoxy compound (A-1)

The epoxy compound (A-1) obtained by the method described in Preparation Example 1 was used.

(ii) other epoxy compounds (IIIB-1)

The bisphenol A liquid epoxy resin, the Shinnidetsu Chemicals make, brand name:YD-128 was used.

(iii) other epoxy compounds (IIIB-2)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(iv) thermocationic polymerization initiator (IIID-4)

Diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate, the San Apro company make, CPI-101A was used.

(v) thermocationic polymerization initiator (IIID-5)

4-methylphenyl-4-(1-methylethyl)phenyliodoniumtetrakis(pentafluorophenyl)borate, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used.

(2) Physical property evaluation

The curable composition obtained as mentioned above was heated on condition of the following, and hardened|cured material was obtained.

(a) Example III6-1

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and was heated by a hot air circulation oven at 60°C for 1 hour, at 90°C for 1 hour, at 190°C for 1 hour, and at 240°C. It heated for 2 hours and obtained hardened|cured material.

(b) Example III6-2

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and was heated at 60°C for 1 hour, at 140°C for 1 hour, at 200°C for 1 hour, and at 240°C by a hot air circulation oven. It heated for 2 hours and obtained hardened|cured material.

(c) Example III6-3

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 100°C for 1 hour, at 140°C for 1 hour, and at 200°C for 2 hours using a hot air circulation oven, got the cargo.

(d) Example III6-4

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 140°C for 1 hour and at 210°C for 2 hours with a hot air circulation oven to obtain a cured product.

(a') Comparative Example III6-1

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 70° C. for 1 hour, at 130° C. for 1 hour, and at 170° C. for 2 hours with a hot air circulation oven, got the cargo.

(b') Comparative Example III6-2

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 80°C for 1 hour, at 140°C for 1 hour, and at 180°C for 2 hours using a hot air circulation oven, got the cargo.

(c') Comparative Example III6-3

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 130° C. for 1 hour, at 150° C. for 1 hour, and at 230° C. for 2 hours with a hot air circulation oven, got the cargo.

(d') Comparative Example III6-4

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 140° C. for 1 hour, at 160° C. for 1 hour, and at 240° C. for 2 hours using a hot air circulation oven, got the cargo.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III2-1. The measurement results are summarized in Table III-7.

III-7. Example III7: Preparation of a curable composition containing an epoxy compound (A-1) and its evaluation (Its 7: Combination with various other epoxy compounds and various thermal cationic polymerization initiators)

(1) Examples III7-1 to III7-8 and Comparative Examples III7-1 to III7-8

Except having changed the composition of the curable composition as shown in Tables III-8 and III-9 using the following components, it carried out similarly to Example III1-1, and obtained the curable composition.

(i) Epoxy compound (A-1)

The epoxy compound (A-1) obtained by the method described in Preparation Example 1 was used.

(ii) other epoxy compounds (IIIB-1)

The bisphenol A liquid epoxy resin, the Shinnidetsu Chemicals make, brand name:YD-128 was used.

(iii) other epoxy compounds (IIIB-2)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(iv) other epoxy compounds (IIIB-8)

Tetramethylene glycol diglycidyl ether and a reagent manufactured by Tokyo Chemical Industry Co., Ltd. were used.

(v) other epoxy compounds (IIIB-9)

Cyclohexanedicarboxylic acid diglycidyl ester and a reagent manufactured by Tokyo Chemical Industry Co., Ltd. were used.

(vi) other epoxy compounds (IIIB-10)

Vinyl cyclohexene dioxide and a reagent manufactured by Sigma Aldorich were used.

(vii) other epoxy compounds (IIIB-14)

Tetrahydroindene diepoxide prepared by the method described in Japanese Patent Laid-Open No. 2012-116390 was used.

(viii) other epoxy compounds (IIIB-16)

A monoepoxy compound prepared by the method described in Preparation Example 4 was used.

(ix) thermocationic polymerization initiator (IIID-1)

Aromatic sulfonium salt: 4-acetoxyphenyl dimethyl sulfonium hexafluoroantimonate, the Sanshin Chemical Co., Ltd. make, brand name:SI-150L was used.

(x) thermocationic polymerization initiator (IIID-2)

4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate, the Sanshin Chemical Co., Ltd. make, brand name:SI-100L was used.

(xi) thermocationic polymerization initiator (IIID-3)

Bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfidebishexafluoroantimonate, the ADEKA company make, Adeka Cruz SP-170 was used.

(2) Physical property evaluation

The curable composition obtained as mentioned above was heated on condition of the following, and hardened|cured material was obtained.

(a) Example III7-1

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 150° C. for 1 hour, and at 200° C. for 2 hours with a hot air circulation oven. got the cargo.

(b) Example III7-2

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 110° C. for 1 hour, at 130° C. for 1 hour, and at 220° C. for 2 hours with a hot air circulation oven, got the cargo.

(c) Example III7-3

The curable composition obtained as mentioned above was poured into a metal mold|die similarly to Example III1-1, and it heated at 100 degreeC for 1 hour and 240 degreeC with a hot air circulation oven for 2 hours, and obtained hardened|cured material.

(d) Example III7-4

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 150°C for 1 hour, at 180°C for 1 hour, and at 210°C for 2 hours using a hot air circulation oven, got the cargo.

(e) Example III7-5

The curable composition obtained as mentioned above was poured into a mold similarly to Example III1-1, and it heated at 120 degreeC for 1 hour and 210 degreeC with a hot air circulation oven for 2 hours, and obtained hardened|cured material.

(f) Example III7-6

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 160° C. for 1 hour, and at 220° C. for 2 hours with a hot air circulation oven. got the cargo.

(g) Example III7-7

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 70° C. for 1 hour, at 120° C. for 1 hour, and at 220° C. for 2 hours using a hot air circulation oven, got the cargo.

(h) Examples III7-8

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 190° C. for 1 hour, and at 240° C. for 2 hours using a hot air circulation oven, got the cargo.

(a') Comparative Example III7-1

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 150 ° C. for 1 hour, 170 ° C. for 1 hour, and 2 at 10 ° C. for 2 hours with a hot air circulation oven, A cured product was obtained.

(b') Comparative Example III7-2

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and heated at 120° C. for 1 hour, at 130° C. for 1 hour, and at 190° C. for 2 hours with a hot air circulation oven. got the cargo.

(c') Comparative Example III7-3

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and was heated at 115°C for 1 hour, at 130°C for 1 hour, at 190°C for 1 hour, at 240°C by means of a hot air circulation oven. It heated for 2 hours and obtained hardened|cured material.

(d') Comparative Example III7-4

The curable composition obtained as mentioned above was poured into a mold similarly to Example III1-1, and it heated at 170 degreeC for 1 hour and 210 degreeC with a hot-air circulation oven for 2 hours, and obtained hardened|cured material.

(e') Comparative Example III7-5

The curable composition obtained as mentioned above was poured into a mold similarly to Example III1-1, and it heated at 120 degreeC for 1 hour and 220 degreeC with a hot-air circulation oven for 2 hours, and obtained hardened|cured material.

(f') Comparative Example III7-6

The curable composition obtained as mentioned above was poured into a mold similarly to Example III1-1, and it heated at 120 degreeC for 1 hour and 220 degreeC with a hot-air circulation oven for 2 hours, and obtained hardened|cured material.

(g') Comparative Example III7-7

The curable composition obtained as described above was poured into a mold in the same manner as in Example III1-1, and was heated by a hot air circulation oven at 80°C for 1 hour, at 120°C for 1 hour, at 240°C for 1 hour, and at 240°C. It heated for 2 hours and obtained hardened|cured material.

(h') Comparative Example III7-8

The curable composition obtained as mentioned above was poured into a mold similarly to Example III1-1, and it heated at 120 degreeC for 1 hour and 140 degreeC with a hot air circulation oven for 2 hours, and obtained hardened|cured material.

The glass transition temperature of the cured product obtained as described above was measured in the same manner as in Example III2-1. The measurement results are summarized in Tables III-8 and III-9.

IV. Embodiments IV of the present invention

IV-1. Example IV1: Preparation of a curable composition containing an epoxy compound (A-3) and its evaluation (their 1: evaluation in the case of using an acid anhydride type curing agent)

(1) Example IV1-1

Preparation of curable composition

The epoxy compound (A-3) obtained as described above, another epoxy compound (IVB-1), an acid anhydride-based curing agent, a curing accelerator, and a compound having a hydroxyl group were mixed so as to have the following composition, and a curable composition was obtained.

<Composition of curable composition>

- Epoxy compound (A-3) 75 parts by mass (epoxy compound (A-3) obtained by the method described in Preparation Example 3 above)

・Other epoxy compound (IVB-1) 25 parts by mass (bisphenol A liquid epoxy resin, manufactured by Shin-Nidetsu Chemical Co., Ltd., trade name: YD-128)

123 parts by mass of acid anhydride curing agent (a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, 0.9 equivalents equivalent to 1 equivalent of the epoxy compound (A-3), manufactured by New Japan Corporation, trade name: MH- 700)

・Cure accelerator (IVC-1) 2 parts by mass (2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Co., Ltd., trade name: 2 E4MZ)

・Compound having a hydroxyl group 　　　5 parts by mass (ethylene glycol, manufactured by Wako Pure Chemical Industries, Ltd., reagent)

The curable composition obtained as mentioned above was heated at 110 degreeC for 1 hour, at 120 degreeC for 2 hours, at 190 degreeC for 1 hour, and at 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

＜＜Performance evaluation＞＞

<Moisture resistance>

The water absorption of the hardened|cured material obtained as mentioned above was measured based on A method described in JIS K7209, and the moisture resistance was evaluated. The measurement results are summarized in Table IV-1.

<Heat resistance>

The glass transition temperature of the cured product obtained as described above was measured with a differential scanning calorimeter (manufactured by Hitachi High-Tech Sciences, trade name: DSC7020) to 30 to 300° C. at 10° C./min. In addition, the glass transition temperature here was measured based on "middle point glass transition temperature: T _mg " described in JIS K7121 "Method for measuring transition temperature of plastics". The measurement results are summarized in Table IV-1.

＜Comprehensive evaluation＞

The comprehensive evaluation of the curable composition obtained in the said Example was evaluated according to the following evaluation criteria. The evaluation results are summarized in Table IV-1.

○: Water absorption less than 0.50% and heat resistance 160 degrees Celsius or more

x: Water absorption is 0.50% or more and/or heat resistance is less than 160 degreeC, and there existed a problem practically.

(2) Examples IV1-2 to IV1-4

Except having changed the composition of the curable composition as shown in Table IV-1, it carried out similarly to Example IV1, and obtained the curable composition.

After obtaining a cured product in the same manner as in Example IV1 from the curable composition obtained as described above, the water absorption and glass transition temperature of the cured product were measured. The measurement results are summarized in Table IV-1.

(3) Comparative Example IV1-1

Except having changed the composition of the curable composition as shown in Table IV-1, it carried out similarly to Example IV1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 100 degreeC for 2 hours and 160 degreeC for 4 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The water absorption and glass transition temperature of the cured product obtained as described above were measured. The measurement results are summarized in Table IV-1.

(4) Comparative Example IV1-2

Except having changed the composition of the curable composition as shown in Table IV-1, it carried out similarly to Example IV1, and obtained the curable composition.

The curable composition obtained as mentioned above was heated at 100 degreeC for 2 hours, 160 degreeC for 2 hours, and 220 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

The water absorption and glass transition temperature of the cured product obtained as described above were measured. The measurement results are summarized in Table IV-1.

Each component used in Table IV-1 for preparation of each curable composition is as follows.

Other epoxy compounds (IVB-2): 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation, brand name: Celoxide 2021P.

IV-2. Example IV2: Preparation of curable composition containing epoxy compound (A-3) and evaluation thereof (2: Combination with other epoxy compounds and acid anhydride-based curing agents)

(1) Examples IV2-1 to IV2-13 and Comparative Examples IV2-1 to IV2-14

Except having changed the composition of the curable composition as shown in Tables IV-2 to IV-4 using the following components, it carried out similarly to Example IV1-1, and obtained the curable composition.

(i) Epoxy compound (A-3)

The epoxy compound (A-3) obtained by the method described in the said preparation example 3 was used.

(ii) other epoxy compounds (IVB-1)

The bisphenol A liquid epoxy resin, the Shinnidetsu Chemicals make, brand name:YD-128 was used.

(iii) other epoxy compounds (IVB-2)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(iv) other epoxy compounds (IVB-3)

A cresol novolak-type epoxy resin, the DIC company make, brand name:N-660 was used.

(v) other epoxy compounds (IVB-4)

A phenol novolak-type epoxy resin, the Shinnidetsu Chemicals make, brand name:YDPN-638 was used.

(vi) other epoxy compounds (IVB-5)

The bisphenol F-type liquid epoxy resin, the Shinnidetsu Sumi-King Chemicals make, brand name:YDF-170 was used.

(vii) other epoxy compounds (IVB-6)

Hydrogenated bisphenol A liquid epoxy resin, the Mitsubishi Chemical Corporation make, brand name:YX8000 was used.

(viii) other epoxy compounds (IVB-7)

Triglycidyl isocyanurate, the Nissan Chemical Industry Co., Ltd. make, brand name: TEPIC-S was used.

(ix) other epoxy compounds (IVB-8)

Tetramethylene glycol diglycidyl ether and a reagent manufactured by Tokyo Chemical Industry Co., Ltd. were used.

(x) other epoxy compounds (IVB-9)

Cyclohexanedicarboxylic acid diglycidyl ester and a reagent manufactured by Tokyo Chemical Industry Co., Ltd. were used.

(xi) other epoxy compounds (IVB-10)

Vinyl cyclohexene dioxide and a reagent manufactured by Sigma Aldorich were used.

(xii) other epoxy compounds (IVB-11)

A 1,2-epoxy-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, the Daicel company make, brand name: EHPE3150 was used.

(xiii) other epoxy compounds (IVB-12)

Limonene dioxide and a reagent manufactured by Sigma Aldorich were used.

(xiv) other epoxy compounds (IVB-13)

(3,3',4,4'-diepoxy)bicyclohexyl, the Daicel company make, brand name: Celoxide 8000 was used.

(xv) other epoxy compounds (IVB-14)

Tetrahydroindene diepoxide prepared by the method described in Japanese Patent Laid-Open No. 2012-116390 was used.

(xvi) other epoxy compounds (IVB-16)

A monoepoxy compound prepared by the method described in Preparation Example 4 was used.

(xvii) acid anhydride curing agent

The mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, the Shin-Nippon Ikas company make, brand name:MH-700 was used.

(xviii) curing accelerator (IVC-1)

2-ethyl-4-methylimidazole, the Shikoku Chemical Co., Ltd. make, brand name:2E4MZ was used.

(xix) hardening accelerator (IVC-2)

1,8-diazabicyclo(5,4,0)undecene-7, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used.

(xx) a compound having a hydroxyl group

Ethylene glycol, the Wako Pure Chemical Industries, Ltd. product, and reagent were used.

(2) Performance evaluation

(Heat resistance of cured product of curable composition)

The curable composition obtained as mentioned above was heated on condition of the following, and hardened|cured material was obtained.

(a) Example IV2-1

The curable composition obtained as mentioned above was heated at 100 degreeC for 1 hour, 170 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(b) Example IV2-2

The curable composition obtained as mentioned above was heated at 100 degreeC for 1 hour, 150 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(c) Example IV2-3

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(d) Example IV2-4

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 130 degreeC for 1 hour, and 160 degreeC for 2 hours with a hot-air circulation oven, and the hardened|cured material was obtained.

(e) Examples IV2-5

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 130 degreeC for 1 hour, and 170 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(f) Examples IV2-6

The curable composition obtained as mentioned above was heated at 100 degreeC for 1 hour, 140 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(g) Example IV2-7

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, at 120 degreeC for 1 hour, at 170 degreeC for 1 hour, and at 230 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(h) Examples IV2-8

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 130 degreeC for 1 hour, and 160 degreeC for 2 hours with a hot-air circulation oven, and the hardened|cured material was obtained.

(i) Examples IV2-9

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, at 120 degreeC for 1 hour, at 170 degreeC for 1 hour, and at 210 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(j) Examples IV2-10

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, 130 degreeC for 1 hour, and 140 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(k) Examples IV2-11

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(l) Examples IV2-12

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, 180 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(m) Examples IV2-13

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour and 180 degreeC with a hot-air circulation oven for 2 hours, and the hardened|cured material was obtained.

(a') Comparative Example IV2-1

The curable composition obtained as mentioned above was heated at 130 degreeC for 1 hour, 160 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(b') Comparative Example IV2-2

The curable composition obtained as mentioned above was heated at 120 degreeC for 1 hour, 150 degreeC for 1 hour, and 170 degreeC for 2 hours with a hot-air circulation oven, and the hardened|cured material was obtained.

(c') Comparative Example IV2-3

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(d') Comparative Example IV2-4

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 130 degreeC for 1 hour, and 160 degreeC for 2 hours with a hot-air circulation oven, and the hardened|cured material was obtained.

(e') Comparative Example IV2-5

The curable composition obtained as mentioned above was heated at 80 degreeC for 1 hour, 130 degreeC for 1 hour, and 170 degreeC for 2 hours with a hot air circulation oven, and the hardened|cured material was obtained.

(f') Comparative Example IV2-6

The curable composition obtained as mentioned above was heated at 100 degreeC for 1 hour, 140 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(g') Comparative Example IV2-7

The curable composition obtained as mentioned above was heated at 60 degreeC for 1 hour, at 110 degreeC for 1 hour, at 160 degreeC for 1 hour, and at 240 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(h') Comparative Example IV2-8

The curable composition obtained as mentioned above was heated at 80 degreeC for 1 hour, 120 degreeC for 1 hour, and 150 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(i') Comparative Example IV2-9

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, at 100 degreeC for 1 hour, at 190 degreeC for 1 hour, and at 240 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(j') Comparative Example IV2-10

The curable composition obtained as mentioned above was heated at 70 degreeC for 1 hour, 130 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(k') Comparative Example IV2-11

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 240 degreeC for 2 hours with a hot-air circulation oven, and hardened|cured material was obtained.

(l') Comparative Example IV2-12

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(m') Comparative Example IV2-13

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour, 140 degreeC for 1 hour, and 180 degreeC for 2 hours with a hot air circulation oven, and hardened|cured material was obtained.

(n') Comparative Example IV2-14

The curable composition obtained as mentioned above was heated at 90 degreeC for 1 hour and 180 degreeC with a hot-air circulation oven for 2 hours, and the hardened|cured material was obtained.

The heat resistance (glass transition temperature) of the cured product obtained as described above was measured in the same manner as in Example IV1-1. The measurement results are summarized in Tables IV-2 to IV-4.

V. EMBODIMENTS OF Aspect V of the Invention

V-1. Example V1: Preparation of curable composition containing an epoxy compound (A-1) or an epoxy compound (A-2) and its evaluation (the 1: Comparison with other epoxy compounds)

(1) Example V1-1

Preparation of curable composition

The epoxy compound (A-1) obtained as mentioned above, a photocationic polymerization initiator (VD-1), and another epoxy compound (VB-2) were mixed so that it might become the following composition, and the curable composition was obtained.

<Composition of curable composition>

25 parts by mass of epoxy compound (A-1) (epoxy compound prepared by the method described in Preparation Example 1)

・Other epoxy compound (VB-2) 　　　 75 parts by mass (bisphenol A liquid epoxy resin, manufactured by Shinnidetsu Chemicals, trade name: YD-128)

・Photocationic polymerization initiator (VD-1) 10 parts by mass (aromatic sulfonium salt: 50% solution of propylene carbonate of diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, manufactured by San Apro, trade name: CPI-100P )

(2) Example V1-2

Preparation of curable composition

A curable composition was obtained in the same manner as in Example V1-1 except that the epoxy compound (A-1) was changed to the epoxy compound (A-2) (the epoxy compound produced by the method described in Preparation Example 2).

(3) Comparative Example V1-1

Except not containing an epoxy compound (A-1) but having made the other epoxy compound (VB-2) 100 mass parts, it carried out similarly to Example V1-1, and obtained the curable composition.

(4) Comparative Example V1-2

Without containing an epoxy compound (A-1), 75 mass parts of other epoxy compounds (VB-2), other epoxy compounds (VB-3) (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane Carboxylate, the Daicel company make, brand name: Celoxide 2021P) Except having set it as 25 mass parts, it carried out similarly to Example V1-1, and obtained the curable composition.

(5) Comparative Example V1-3

In the same manner as in Example V1-1, except that the epoxy compound (A-1) was not contained and the other epoxy compound (VB-2) was 25 parts by mass and the other epoxy compound (VB-3) was 75 parts by mass. A curable composition was obtained.

(6) Comparative Example V1-4

A curable composition was obtained in the same manner as in Example V1-1 except that the epoxy compound (A-1) was changed to another epoxy compound (VB-1) (dicyclopentadiene diepoxide) represented by the following formula. .

(7) Performance evaluation of curable composition

<Heat resistance (weight loss temperature)>

The curable compositions obtained in Examples V1-1 and V1-2 and Comparative Examples V1-1 to V1-4 were applied to a thickness of 50 µm on a glass substrate, and the accumulated light quantity was 3,000 mJ/cm ² UV light was irradiated at room temperature (23° C.) to cure the curable composition. Next, the cured product was collected from the glass substrate, and the cured product was measured using a differential calorimetry simultaneous measurement device (Hitachi Hi-Tech Science, trade name: TG/DTA7200), and about 10 mg of the cured product was measured from room temperature to 550° C. under dry air. The temperature was raised at a constant rate at 10°C/min, and the 1% weight loss temperature, 3% weight loss temperature, 5% weight loss temperature, and 10% weight loss temperature were measured. The measurement results are summarized in Table V-1.

V-2. Example V2: Preparation and evaluation of curable composition containing epoxy compound (A-1) or epoxy compound (A-2) (2: comparison with other epoxy compounds)

(1) Example V2-1

Preparation of curable composition

The epoxy compound (A-1) obtained as mentioned above, a photocationic polymerization initiator (VD-1), and another epoxy compound (VB-3) were mixed so that it might become the following composition, and the curable composition was obtained.

<Composition of curable composition>

25 parts by mass of epoxy compound (A-1) (epoxy compound prepared by the method described in Preparation Example 1)

・Other epoxy compound (VB-3) 　　　 75 parts by mass (3',4'-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate, manufactured by Daicel, trade name: Celoxide 2021P)

・Photocationic polymerization initiator (VD-1) 10 parts by mass (aromatic sulfonium salt: 50% solution of propylene carbonate of diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, manufactured by San Apro, trade name: CPI-100P )

(2) Example V2-2

Preparation of curable composition

A curable composition was obtained in the same manner as in Example V2-1 except that the epoxy compound (A-1) was changed to the epoxy compound (A-2) (the epoxy compound produced by the method described in Preparation Example 2).

(3) Comparative Example V2-1

A curable composition was obtained in the same manner as in Example V2-1, except that the epoxy compound (A-1) was not contained and the other epoxy resin (VB-3) was set to 100 parts by mass.

(4) Comparative Example V2-2

Except having changed the epoxy compound (A-1) into another epoxy compound (VB-1) (dicyclopentadiene diepoxide), it carried out similarly to Example V2-1, and obtained the curable composition.

(5) Performance evaluation of curable composition

<Heat resistance (weight loss temperature)>

The curable compositions obtained in Examples V2-1 and V2-2 and Comparative Examples V2-1 and V2-2 were applied to a thickness of 50 µm on a glass substrate, and the amount of accumulated light was 3,000 mJ/cm ² Ultraviolet rays Light was irradiated at room temperature (23 degreeC), and the curable composition was hardened. Next, the cured product was collected from the glass substrate, and the cured product was measured using a differential calorimetry simultaneous measurement device (Hitachi Hi-Tech Science, trade name: TG/DTA7200), and about 10 mg of the cured product was measured from room temperature to 550° C. under dry air. The temperature was raised at a constant rate at 10°C/min, and the 1% weight loss temperature, 3% weight loss temperature, 5% weight loss temperature, and 10% weight loss temperature were measured. The measurement results are summarized in Table V-2.

V-3. Example V3: Preparation of curable composition containing epoxy compound (A-1) or epoxy compound (A-2) and evaluation thereof (3: combination of octacene compound and photocationic polymerization initiator thereof)

(1) Example V3-1

Preparation of curable composition

The epoxy compound (A-1) obtained as mentioned above, a photocationic polymerization initiator (VD-1), and an oxetane compound (VC-1) were mixed so that it might become the following composition, and the curable composition was obtained.

<Composition of curable composition>

25 parts by mass of epoxy compound (A-1) (epoxy compound prepared by the method described in Preparation Example 1)

・Oxetane compound (VC-1) 75 parts by mass (1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, manufactured by Toagosei Co., Ltd., brand name: Aronoxetane OXT-121)

・Photocationic polymerization initiator (VD-1) 10 parts by mass (aromatic sulfonium salt: 50% solution of propylene carbonate of diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, manufactured by San Apro, trade name: CPI-100P )

(2) Example V3-2

Preparation of curable composition

A curable composition was obtained in the same manner as in Example V3-1 except that the epoxy compound (A-1) was changed to the epoxy compound (A-2) (the epoxy compound produced by the method described in Preparation Example 2).

(3) Comparative Example V3-1

Preparation of curable composition

Except having changed the epoxy compound (A-1) into another epoxy compound (VB-2), it carried out similarly to Example V3-1, and obtained the curable composition.

(4) Comparative Example V3-2

Preparation of curable composition

Except having changed the epoxy compound (A-1) into another epoxy compound (VB-3), it carried out similarly to Example V3-1, and obtained the curable composition.

(5) Performance evaluation of curable composition

<Heat resistance (weight loss temperature)>

The curable compositions obtained in Examples V3-1 and V3-2 and Comparative Examples V3-1 and V3-2 were applied to a thickness of 50 μm on a glass substrate, and the amount of accumulated light was 3,000 mJ/cm ² Ultraviolet rays Light was irradiated at room temperature (23 degreeC), and the curable composition was hardened. Next, the cured product was collected from the glass substrate, and the cured product was measured using a differential calorimetric simultaneous measurement device (Hitachi Hi-Tech Science, trade name: TG/DTA7200), and about 10 mg of the cured product was measured from room temperature to 550° C. under dry air. The temperature was raised at a constant rate at 10°C/min, and the 1% weight loss temperature, 3% weight loss temperature, 5% weight loss temperature, and 10% weight loss temperature were measured. The measurement results are summarized in Table V-3.

V-4. Example V4: Preparation and evaluation of curable composition containing epoxy compound (A-1) or epoxy compound (A-2) (its 4: combination with other epoxy compounds and photocationic polymerization initiators)

(1) Example V4-1

Preparation of curable composition

The epoxy compound (A-1) obtained as mentioned above, a photocationic polymerization initiator (VD-1), and another epoxy compound (VB-16) were mixed so that it might become the following composition, and the curable composition was obtained.

<Composition of curable composition>

25 parts by mass of epoxy compound (A-1) (epoxy compound prepared by the method described in Preparation Example 1)

・Other epoxy compound (VB-16) 75 parts by mass (1,2-epoxy-4-vinylcyclohexane, manufactured by Daicel, trade name: Celoxide 2000)

・Photocationic polymerization initiator (VD-1) 10 parts by mass (aromatic sulfonium salt: 50% solution of propylene carbonate of diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, manufactured by San Apro, trade name: CPI-100P )

(2) Example V4-2

Preparation of curable composition

A curable composition was obtained in the same manner as in Example V3-1 except that the epoxy compound (A-1) was changed to the epoxy compound (A-2) (the epoxy compound produced by the method described in Preparation Example 2).

(3) Comparative Example V4-1

Preparation of curable composition

Except having changed the epoxy compound (A-1) into another epoxy compound (VB-2), it carried out similarly to Example V3-1, and obtained the curable composition.

(4) Comparative Example V4-2

Preparation of curable composition

Except having changed the epoxy compound (A-1) into another epoxy compound (VB-3), it carried out similarly to Example V3-1, and obtained the curable composition.

(5) Performance evaluation of curable composition

<Heat resistance (weight loss temperature)>

The curable compositions obtained in Examples V4-1 and V4-2 and Comparative Examples V4-1 and V4-2 were applied to a thickness of 50 μm on a glass substrate, and the amount of accumulated light was 3,000 mJ/cm ² Ultraviolet rays Light was irradiated at room temperature (23 degreeC), and the curable composition was hardened. Next, the cured product was collected from the glass substrate, and the cured product was measured using a differential calorimetry simultaneous measurement device (Hitachi Hi-Tech Science, trade name: TG/DTA7200), and about 10 mg of the cured product was measured from room temperature to 550° C. under dry air. The temperature was raised at a constant rate at 10°C/min, and the 1% weight loss temperature, 3% weight loss temperature, 5% weight loss temperature, and 10% weight loss temperature were measured. The measurement results are summarized in Table V-4.

V-5. Example V5: Preparation of curable composition containing epoxy compound (A-1) or epoxy compound (A-2) and its evaluation (The 5: Combination of various other epoxy compounds and photocationic polymerization initiators)

(1) Examples V5-1 to V5-10 and Comparative Examples V5-1 to V5-6

Except having changed the composition of the curable composition as shown in Tables V-5 to V-7 using the following components, it carried out similarly to Example V1-1, and obtained the curable composition.

(i) Epoxy compound (A-1)

The epoxy compound prepared by the method described in Preparation Example 1 was used.

(ii) Epoxy compound (A-2)

The epoxy compound prepared by the method described in Preparation Example 2 was used.

(iii) other epoxy compounds (VB-3)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(iv) other epoxy compounds (VB-6)

The bisphenol F-type liquid epoxy resin, the Shinnidetsu Sumi-King Chemicals make, brand name:YDF-170 was used.

(v) other epoxy compounds (VB-7)

Hydrogenated bisphenol A liquid epoxy resin, the Mitsubishi Chemical Corporation make, brand name:YX8000 was used.

(vi) other epoxy compounds (VB-9)

Tetramethylene glycol diglycidyl ether and a reagent manufactured by Tokyo Chemical Industry Co., Ltd. were used.

(vii) other epoxy compounds (VB-10)

Cyclohexanedicarboxylic acid diglycidyl ester and a reagent manufactured by Tokyo Chemical Industry Co., Ltd. were used.

(viii) other epoxy compounds (VB-12)

A 1,2-epoxy-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, the Daicel company make, brand name: EHPE3150 was used.

(ix) other epoxy compounds (VB-17)

A monoepoxy compound prepared by the method described in Preparation Example 4 was used.

(x) photocationic polymerization initiator (VD-1)

The propylene carbonate 50% solution of diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, the San Apro company make, brand name: CPI-100P was used.

(2) Performance evaluation of curable composition

<Heat resistance (weight loss temperature)>

The curable compositions obtained in Examples V5-1 to V5-10 and Comparative Examples V5-1 to V5-6 were applied to a thickness of 50 µm on a glass substrate, and UV rays so that the ^{accumulated light amount was 3,000 mJ/cm 2} Light was irradiated at room temperature (23 degreeC), and the curable composition was hardened. Next, the cured product was collected from the glass substrate, and the cured product was measured using a differential calorimetric simultaneous measurement device (Hitachi Hi-Tech Science, trade name: TG/DTA7200), and about 10 mg of the cured product was measured from room temperature to 550° C. under dry air. The temperature was raised at a constant rate at 10°C/min, and the 1% weight loss temperature, 3% weight loss temperature, 5% weight loss temperature, and 10% weight loss temperature were measured. The measurement results are summarized in Tables V-5 to V-7.

V-6. Example V6: Preparation of a curable composition containing an epoxy compound (A-1) or an epoxy compound (A-2) and evaluation thereof (The 6: Combination of various oxetane compounds and photocationic polymerization initiators)

(1) Example V6-1 and Comparative Example V6-1

Except having changed the composition of the curable composition as shown in Table V-8 using the following components, it carried out similarly to Example V1-1, and obtained the curable composition.

(i) Epoxy compound (A-2)

The epoxy compound prepared by the method described in Preparation Example 2 was used.

(ii) other epoxy compounds (VB-3)

3',4'-epoxycyclohexylmethyl-3,4- epoxycyclohexanecarboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(iii) oxetane compound (VC-3)

Di[(3-ethyl-3-oxetanyl)methyl]ether, the Toagosei company make, brand name: Aronoxetane OXT-221 was used.

(iv) photocationic polymerization initiator (VD-1)

The propylene carbonate 50% solution of diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, the San Apro company make, brand name: CPI-100P was used.

(2) Performance evaluation of curable composition

<Heat resistance (weight loss temperature)>

The curable composition obtained in Example V6-1 and Comparative Example V6-1 was applied to a thickness of 50 μm on a glass substrate, and ultraviolet light was applied at room temperature (23° C.) so that the ^{accumulated light amount was 3,000 mJ/cm 2 .} It was irradiated to cure the curable composition. Next, the cured product was collected from the glass substrate, and the cured product was measured using a differential calorimetry simultaneous measurement device (Hitachi Hi-Tech Science, trade name: TG/DTA7200), and about 10 mg of the cured product was measured from room temperature to 550° C. under dry air. The temperature was raised at a constant rate at 10°C/min, and the 1% weight loss temperature, 3% weight loss temperature, 5% weight loss temperature, and 10% weight loss temperature were measured. The measurement results are summarized in Table V-8.

V-7. Example V7: Preparation and evaluation of curable composition containing epoxy compound (A-1) or epoxy compound (A-2) (its 7: Combination with various photocationic polymerization initiators)

(1) Examples V7-1 to V7-3 and Comparative Examples V7-1 and V7-2

Except having changed the composition of the curable composition as shown in Table V-9 using the following components, it carried out similarly to Example V1-1, and obtained the curable composition.

(i) Epoxy compound (A-1)

The epoxy compound prepared by the method described in Preparation Example 1 was used.

(ii) Epoxy compound (A-2)

The epoxy compound prepared by the method described in Preparation Example 2 was used.

(iii) other epoxy compounds (VB-3)

3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate, the Daicel company make, brand name: Celoxide 2021P was used.

(iv) photocationic polymerization initiator (VD-2)

Diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate, the San Apro company make, CPI-101A was used.

(v) photocationic polymerization initiator (VD-3)

Bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfidebishexafluoroantimonate, the ADEKA company make, Adeka Cruz SP-170 was used.

(2) Performance evaluation of curable composition

<Heat resistance (weight loss temperature)>

The curable compositions obtained in Examples V7-1 to V7-3 and Comparative Examples V7-1 and V7-2 were applied to a thickness of 50 μm on a glass substrate, and UV rays so that the ^{accumulated light amount was 3,000 mJ/cm 2} Light was irradiated at room temperature (23 degreeC), and the curable composition was hardened. Next, the cured product was collected from the glass substrate, and the cured product was measured using a differential calorimetry simultaneous measurement device (Hitachi Hi-Tech Science, trade name: TG/DTA7200), and about 10 mg of the cured product was measured from room temperature to 550° C. under dry air. The temperature was raised at a constant rate at 10°C/min, and the 1% weight loss temperature, 3% weight loss temperature, 5% weight loss temperature, and 10% weight loss temperature were measured. The measurement results are summarized in Table V-9.

Claims (13)

Epoxy compound represented by following formula (1):

(During the meal,
A represents CR ¹⁷ R ¹⁸ ,
B represents CR ¹⁹ R ²⁰ ,
R ¹ to R ²⁰ each independently represent a substituent selected from the group consisting of hydrogen, an alkyl group and an alkoxy group,
n is 0 or 1,
However, when n is 0, m is 1, and when n is 1, m is 0.)
And, a thermocationic polymerization initiator, or an acid anhydride-based curing agent, and a curable composition comprising one selected from the group consisting of a curing accelerator. The method according to claim 1,
Curable composition which further contains 1 type(s) or 2 or more types selected from the group which consists of an epoxy compound other than the epoxy compound represented by said Formula (1), an oxetane compound, and vinyl ether. The method according to claim 1,
The thermal cationic polymerization initiator is selected from the group consisting of an aromatic sulfonium salt-based thermal cationic polymerization initiator, an aromatic iodonium salt-based thermal cationic polymerization initiator, and an aluminum complex-based thermal cationic polymerization initiator. 4. The method according to claim 3,
The curable composition wherein the thermal cationic polymerization initiator is an aromatic sulfonium salt-based thermal cationic polymerization initiator. 3. The method according to claim 2,
When the content of the thermal cationic polymerization initiator does not contain any of an epoxy compound other than the epoxy compound represented by the formula (1), an oxetane compound, and a vinyl ether, the curable composition is contained in the curable composition It is 0.1-15 mass parts with respect to 100 mass parts of epoxy compounds represented by said Formula (1), The said curable composition is epoxy compounds other than the epoxy compound represented by said Formula (1), an oxetane compound, and vinyl ether In the case of including one or two or more selected from the group consisting of It is 0.1-15 mass parts with respect to 100 mass parts of total amounts of curable composition. 3. The method according to claim 2,
When the content of the acid anhydride curing agent does not contain an epoxy compound other than the epoxy compound represented by the formula (1), the curable composition is an epoxy represented by the formula (1) contained in the curable composition. It is 0.6-1.2 equivalent with respect to 1 equivalent of compound, and when the said curable composition contains epoxy compounds other than the epoxy compound represented by the said Formula (1), the epoxy compound represented by the said Formula (1), and its said The curable composition which is 0.6-1.2 equivalent with respect to 1 equivalent of the mixture of the epoxy compound which consists of epoxy compounds other than the epoxy compound represented by Formula (1). 7. The method of claim 6,
Epoxy compound 100 represented by the formula (1) contained in the curable composition when the content of the curing accelerator does not contain an epoxy compound other than the epoxy compound represented by the formula (1) in the curable composition. It is 0.1-10 mass parts with respect to mass part, and when the said curable composition contains epoxy compounds other than the epoxy compound represented by the said Formula (1), the epoxy compound represented by the said Formula (1), and its said The curable composition which is 0.1-10 mass parts with respect to 100 mass parts of total amounts of epoxy compounds other than the epoxy compound represented by Formula (1). The method according to claim 1,
The curable composition, wherein the curing accelerator is an imidazole-based curing accelerator. The method according to claim 1,
The curable composition which further contains the compound which has a hydroxyl group. 10. The method according to any one of claims 1 to 9,
The curable composition whose content of the epoxy compound represented by said Formula (1) is 10-99 mass %. 8. The method of any one of claims 2, 5, 6, and 7,
Epoxy compounds other than the epoxy compound represented by the formula (1) are selected from the group consisting of glycidyl ether-type epoxides, glycidyl ester-type epoxides, and alicyclic epoxides. The manufacturing method of hardened|cured material including the process of hardening the curable composition of any one of Claims 1-9. Hardened|cured material of the curable composition in any one of Claims 1-9.

Images